( 12 ) United States Patent ( 10 ) Patent No .: US 11,011,781 B2 Yamada Et Al

US011011781B2

( 12 ) United States Patent ( 10 ) Patent No .: US 11,011,781 B2 Yamada et al . ( 45 ) Date of Patent : May 18 , 2021

( 54 ) NONAQUEOUS ELECTROLYTE (51 ) Int . Ci . SECONDARY BATTERY HOIM 10/0568 ( 2010.01 ) HOIM 10/0569 ( 2010.01 ) ( 71 ) Applicants : THE UNIVERSITY OF TOKYO , (Continued ) Tokyo ( JP ) ; KABUSHIKI KAISHA ( 52 ) U.S. CI . TOYOTA JIDOSHOKKI, Kariya ( JP ) CPC HOIM 10/0568 ( 2013.01 ) ; HOIM 4/587 ( 2013.01 ) ; HOIM 10/0525 ( 2013.01 ) ; ( 72 ) Inventors : Atsuo Yamada, Tokyo ( JP ) ; Yuki (Continued ) Yamada , Tokyo ( JP ) ; Yoshihiro ( 58 ) Field of Classification Search Nakagaki , Kariya ( JP ) ; Tomoyuki CPC HO1M 10/0568 ; HO1M 10/0525 ; HOLM Kawai, Kariya ( JP ) ; Yuki Hasegawa , 10/0569 ; HO1M 4/587 Kariya ( JP ) ; Kohei Mase , Kariya ( JP ) ; See application file for complete search history . Nobuhiro Goda , Kariya ( JP ) ( 56 ) References Cited ( 73 ) Assignees : THE UNIVERSITY OF TOKYO , U.S. PATENT DOCUMENTS Tokyo ( JP ) ; KABUSHIKI KAISHA TOYOTA JIDOSHOKKI, Kariya ( JP ) 5,607,485 A * 3/1997 Gozdz CO8J 9/28 29 / 623.5 ( * ) Notice : Subject to any disclaimer , the term of this 6,274,271 B1 8/2001 Koshiba et al . patent is extended or adjusted under 35 ( Continued ) U.S.C. 154 ( b ) by 465 days . FOREIGN PATENT DOCUMENTS ( 21 ) Appl. No .: 15 / 024,415 CA 2625271 A1 9/2009 CN 101164189 A 4/2008 ( 22 ) PCT Filed : Sep. 25 , 2014 ( Continued ) ( 86 ) PCT No .: PCT / JP2014 / 004911 OTHER PUBLICATIONS $ 371 ( c ) ( 1 ) , Communication dated Jul. 19 , 2018 from the Japanese Patent Office ( 2 ) Date : Mar. 24 , 2016 in Japanese application No. 2015-172591 . ( Continued ) ( 87 ) PCT Pub . No .: WO2015 / 045387 Primary Examiner Jimmy Vo PCT Pub . Date : Apr. 2 , 2015 ( 74 ) Attorney, Agent, or Firm — Sughrue Mion , PLLC ( 65 ) Prior Publication Data ( 57 ) ABSTRACT US 2016/0226100 A1 Aug. 4 , 2016 An electrolytic solution of a nonaqueous electrolyte second ary battery contains a metal salt , and an organic solvent (30 ) Foreign Application Priority Data having a heteroatom and satisfies Is > Io , when an intensity of an original peak of the solvent is represented as lo and an Sep. 25 , 2013 ( JP ) JP2013-198282 intensity of a peak resulting from shifting of the original Sep. 25 , 2013 ( JP ) JP2013-198283 peak is represented as Is . For the negative electrode, ( 1 ) a ( Continued ) ( Continued )

4500

4000 01s

35000

3000

secondcount)intensity/Peak( 2500 2000 !

15001

1000

500

296 294 292 290 288 286 284 282 280 Bond energy ( eV ) EB1 ( 4.5M LFSA , AN E82 ( 4.2M LITFSA : AN ) : C61 ( 1M VPF6 / EC + DEC ( 3: 7) ] US 11,011,781 B2 Page 2 graphite whose G / D ratio of G -band and D - band peaks in a 2011/01832 18 A1 7/2011 Odani et al . 2011/0287325 A1 11/2011 Zaghib et al . Raman spectrum is not lower than 3.5 ; ( 2 ) a carbon material 2011/0318647 Al 12/2011 Lee et al . whose crystallite size , calculated from a half width of a peak 2012/0135308 Al 5/2012 Loveridge et al . appearing at 20 = 20 degrees to 30 degrees in a X - ray 2012/0171580 A1 7/2012 Iwaya et al . diffraction profile is not larger than 20 nm ; ( 3 ) silicon 2012/0316716 Al 12/2012 Odani et al . 2013/0022861 A1 1/2013 Miyagi et al . element and / or tin element; ( 4 ) a metal oxide configured to 2013/0164618 A1 * 6/2013 Konishi HOTM 4/133 occlude and release lithium ions ; or ( 5 ) a graphite whose 429/217 ratio ( long axis / short axis ) is 1 to 5 . 2014/0242458 Al 8/2014 Abe et al . 2015/0050563 Al 2/2015 Yamada et al . 21 Claims , 64 Drawing Sheets 2015/0243936 A1 8/2015 Miyagi et al . 2017/0040593 A1 2/2017 Miyagi et al . FOREIGN PATENT DOCUMENTS ( 30 ) Foreign Application Priority Data CN 101385183 A 3/2009 CN 101292389 A 9/2010 Sep. 25 , 2013 ( JP ) JP2013-198284 CN 101292389 B 9/2010 Sep. 25 , 2013 ( JP ) JP2013-198285 CN 101882696 A 11/2010 Sep. 25 , 2013 ( JP ) JP2013-198599 CN 102576905 A 7/2012 JP2014-065799 EP 1380569 A1 4/2004 Mar. 27 , 2014 ( JP ) EP 1 906 481 A1 4/2008 Mar. 27 , 2014 ( JP ) JP2014-065817 JP 60-036315 A 2/1985 Sep. 12 , 2014 ( JP) JP2014-186338 JP 07-320783 A 12/1995 Sep. 12 , 2014 (JP ) JP2014-186339 JP 10027733 A 1/1998 Sep. 12 , 2014 ( JP ) JP2014-186340 JP 10-069922 A 3/1998 JP2014-186341 JP 11031637 A 2/1999 Sep. 12 , 2014 (JP ) JP 11-154513 A 6/1999 Sep. 12 , 2014 ( JP ) JP2014-186342 JP 2000077100 A 3/2000 JP 2001-507043 A 5/2001 ( 51 ) Int . Ci . JP 2001-266878 A 9/2001 HOIM 4/587 ( 2010.01 ) JP 2002-203562 A 7/2002 JP 2002-523879 A 7/2002 HOIM 10/0525 ( 2010.01 ) JP 2003268053 A 9/2003 ( 52 ) U.S. Ci . JP 2004-511887 A 4/2004 ??? HOIM 10/0569 ( 2013.01 ) ; HOLM JP 2004111294 A 4/2004 2300/0025 ( 2013.01 ) ; HOIM 2300/0028 JP 2004511887 A 4/2004 JP 2005243321 A 9/2005 ( 2013.01 ) JP 2006073434 A 3/2006 JP 2006513554 A 4/2006 ( 56 ) References Cited JP 2006-164759 A 6/2006 JP 2006-164960 A 6/2006 U.S. PATENT DOCUMENTS JP 2006-324167 A 11/2006 JP 2007019027 A 1/2007 6,294,289 B1 * 9/2001 Fanta C07C 317/44 JP 2007091573 A 4/2007 429/188 JP 2007115671 A 5/2007 6,340,716 B1 1/2002 Armand et al . JP 2007243111 A 9/2007 6,365,301 B1 * 4/2002 Michot C07C 45/46 JP 2008010613 A 1/2008 359/270 JP 2008501220 A 1/2008 6,420,070 B1 7/2002 Kasamatsu et al . JP 2008-047479 A 2/2008 7,622,226 B2 11/2009 Takahashi JP 2008053207 A 3/2008 8,076,026 B2 12/2011 Muthu et al . JP 2009026514 A 2/2009 8,148,017 B2 4/2012 Matsui et al . JP 2009-117334 A 5/2009 8,257,865 B2 9/2012 Suzuki et al. JP 2009123474 A 6/2009 8,568,931 B2 10/2013 Iwaya et al . JP 2010-097802 A 4/2010 8,945,780 B2 2/2015 Odani et al . JP 2010073489 A 4/2010 8,986,880 B2 3/2015 Odani et al . JP 2010225539 A 10/2010 9,017,881 B2 4/2015 Lee et al . JP 2011-054298 A 3/2011 9,590,239 B2 3/2017 Abe et al . JP 2011077051 A 4/2011 2002/0013381 Al 1/2002 Armand et al . JP 2011-119053 A 6/2011 2003/0195269 Al 10/2003 Armand et al . JP 2011146359 A 7/2011 2004/0094741 A1 5/2004 Sato et al . JP 2011-150958 A 8/2011 2004/0106047 Al 6/2004 Mie et al . JP 2011216480 A 10/2011 2005/0158631 Al 7/2005 Armand et al . JP 4862555 B2 1/2012 2005/0221170 A1 10/2005 Takeuchi et al. JP 2012-033268 A 2/2012 2006/0127764 A1 6/2006 Chen et al . JP 2012504314 A 2/2012 2007/0031729 A1 2/2007 Sato et al . JP 2012-160345 A 8/2012 2007/0205388 A1 9/2007 Armand et al . JP 2013016456 A 1/2013 2008/0076021 A1 3/2008 Takahashi JP 2013-065493 A 4/2013 2008/03 14482 A1 12/2008 Suzuki et al . JP 5177211 B2 4/2013 2009/0023074 Al 1/2009 Matsui et al. JP 2013065575 A 4/2013 2009/0130565 A1 5/2009 Matsui et al. JP 2013-093242 A 5/2013 2009/0176164 Al 7/2009 Matsui et al . JP 2013082581 A 5/2013 2009/0301866 Al 12/2009 Zaghib et al . JP 2013134922 A 7/2013 2010/0015514 Al 1/2010 Miyagi et al. JP 2013137873 A 7/2013 2010/0075229 Al 3/2010 Atsuki et al . JP 2013145724 A 7/2013 2011/0159379 Al * 6/2011 Matsumoto HO1M 4/0421 JP 2013149477 A 8/2013 429/326 JP 2013-179067 A 9/2013 US 11,011,781 B2 Page 3

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WO 2006049027 A1 5/2006 Communication dated Mar. 3 , 2017 issued by the Canadian Intel WO 2006/115023 A1 11/2006 lectual Property Office in counterpart Canadian Application No. WO 2007125682 A1 11/2007 2,925,379 . WO 2010130976 A1 11/2010 U.S. Appl. No. 15 / 024,380 , Atsuo Yamada , filed Mar. 24 , 2016 . WO 2011111364 A1 9/2011 U.S. Appl. No. 15 / 024,436 , Atsuo Yamada, filed Mar. 24 , 2016 . U.S. Appl. No. 15 / 024,418 , Atsuo Yamada, filed Mar. 24 , 2016 . OTHER PUBLICATIONS U.S. Appl. No. 15 / 024,654 , Atsuo Yamada , filed Mar. 24 , 2016 . Communication dated Mar. 8 , 2017 , issued from the European Communication dated Jul. 24 , 2018 from the Japanese Patent Office Patent Office in corresponding European Application No. 14848198 . in counterpart Japanese application No. 2015-172547 . 9 . Communication dated Jul. 24 , 2018 from the Japanese Patent Office Communication dated Aug. 30 , 2018 from the Japanese Patent in Japanese application No. 2015-172553 . Office in application No. 2015-172655 . Communication dated Jul. 24 , 2018 from the Japanese Patent Office Communication dated Sep. 20 , 2018 from the Japanese Patent in Japanese application No. 2016-131137 . Office in application No. 2015-192458 . Communication dated Jul. 24 , 2018 from the Japanese Patent Office Furukawa et al . , “ Li - Air Battery Using Stabilized Acetonitrile in Japanese application No. 2016-131147 . Electrokyte ” , Abstracts the 53rd Battery Symposium in Japan , The Notification of Reasons for Refusal issued by the Japanese Patent Committee of Battery Technology, The Electrochemical Society of Office in JP 2015-192458 , a divisional of JP 2014-186298 , dated Japan , 2012 , p . 455 ( 3 pages ) . Nov. 20 , 2018 . Communication dated Jun . 1 , 2017 from the State Intellectual Seo , et al ., “ Electrolyte Solvation and Ionic Association II . 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Linear Carbonate Solvents ” , Journal of the Electrochemical Society , 25 , No. 21 . U.S.A. , vol . 158 , issue 2 , 2011 , pp . A74 - A82 ( 9 pages ) . Makoto Yaegashi, “ Developing New Functions of Organic Solu Communication dated Apr. 11 , 2019 , from the Japanese Patent tions by Controlling Coordination State of Solvents ” , Abstracts the Office in application No. 2015-192458 . 53rd Battery Symposium in Japan , The Committee of Battery Communication dated Apr. 11 , 2019 , from the Japanese Patent Technology, The Electrochemical Society of Japan , Nov. 13 , 2012 , Office in application No. 2015-172553 . pp . 507 . Communication dated May 2 , 2019 from the United States Patent International Search Report for PCT / JP2014 / 004911 dated Dec. 9 , and Trademark Office in U.S. Appl. No. 15 / 993,729 . 2014 . Yamada, Yuki et al . , “ A Superconcentrated Ether Electrolyte for Written Opinion for PCT / JP2014 / 004911 dated Dec. 9 , 2014 . Fast -Charging Li - Ion Batteries ” , The Royal Society of Chemistry : Japanese Office Action for JP 2014-186338 dated Apr. 2 , 2015 . Chemical Communications, vol . 49 , No. 95 , 2013 , pp . 11194-11196 , Japanese Office Action for JP 2014-186339 dated Apr. 2 , 2015 . doi : 10.1039 / c3cc46665e ( 3 pages ) . Japanese Office Action for JP 2014-186340 dated Dec. 2 , 2014 . Communication dated Aug. 14 , 2019 from the United States Patent Japanese Office Action for JP 2014-186341 dated Dec. 2 , 2014 . and Trademark Office in U.S. Appl. No. 15 / 024,380 . Japanese Office Action for JP 2014-186342 dated Apr. 2 , 2015 . Communication dated Nov. 15 , 2019 , from United States Patent and Jun - ichi Yamaki, “ Thermal Stability of Materials Used in Lithium Trademark Office in U.S. Appl. No. 15 / 993,729 . Ion Cells ” , Netsu Sokutei 30 ( 1 ) 3-8 , ( 2003 ) The Japan Society of Communication dated Mar. 3 , 2020 , from United States Patent and Calorimetry and Thermal Analysis ., p . 3 only. Trademark Office in U.S. Appl. No. 15 / 024,436 . Yuki Yamada et al . , “ Electrochemical Lithium Intercalation into Wang et al ., “ Conversion of carbohydrates into 5 - hydroxymethylfurfural Graphite in Dimethyl Sulfoxide -Based Electrolytes : Effect of Solva in an advanced single - phase reaction system consisting of water and tion Structure of Lithium Ion ,” Journal of Physical Chemistry , 2010 , 1,2 - dimethoxyethane ”, RSC Advances, 2015 , vol . 5 , No. 102 , pp . vol . 114 , p . 11680-11685 ( 3 pages total ). 84014-84021 ( 8 pages total ) . Han et al . , “ Lithium bis ( flourosulfonyl) imide ( LiFSI ) as conducting Communication dated Apr. 13 , 2020 , from United States Patent and salt for nonaqueous liquid electrolytes for lithium - ion batteries: Trademark Office in U.S. Appl. No. 15 / 024,380 ( 16 pages total ) . Physiochemical and electrochemical properties ,” Journal of Power SciFinder — CAS Registry No. 213195-23-4 ” . 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( 56 ) References Cited Communication dated Jul. 10 , 2017 , from United States Patent and Trademark Office in U.S. Appl. No. 15 / 024,654 . OTHER PUBLICATIONS Communication dated Mar. 7 , 2018 , from United States Patent and < URL : https://scifinder.cas.org/scifinder/view/link_v1/substance . Trademark Office in U.S. Appl. No. 15 / 024,436 . html? I = t7c60yhXV6u1SNfs -Mvwca4zCgqKkIZY3EVcwfP34mLvcIP_ Communication dated Aug. 31 , 2018 , from United States Patent and r07WqVQFqvw3k1FL > . ( Year: 2020 ) ( 3 pages total ). Trademark Office in U.S. Appl. No. 15 / 024,380 . Communication dated Oct. 8 , 2020 , from the United States Patent Communication dated Jan. 24 , 2019 , from United States Patent and and Trademark Office in U.S. Appl. No. 15 / 024,380 . Trademark Office in U.S. Appl. No. 15 / 024,380 . Kazuki Yoshida et al . , “ Electrode Kinetics and Ion Transport Communication dated Jan. 31 , 2019 , from United States Patent and Mechanism in Glyme -Li salts Complexes ” , battery debate lecture Trademark Office in U.S. Appl. No. 15 / 024,418 . gists, Japan , and Inaba, In Committee of Battery Technology, Communication dated Aug. 24 , 2017 , from Korean Intellectual Electrochemical Society of Japan , 2013 , with restriction of p . 160 Property Office in application No. 10-2016-7010618 . (6 pages) . Akihiro Orita , “ Development of high safety energy devices with Communication dated Aug. 22 , 2017 , from Korean Intellectual ionic liquids and proposals for new electrochemical reaction mod Property Office in application No. 10-2016-7010614 . els ” , National University Corporation Yokohama National Univer Communication dated Sep. 28 , 2017 , from Korean Intellectual sity graduate school engineering prefecture With restriction of Property Office in counterpart application No. 10-2016-7010615 . doctoral dissertation , Japan , Sep. 24 , 2012 , shell No. 1491 p . Communication dated Aug. 24 , 2017 , from Korean Intellectual 101-103 ( 9 pages ) . Property Office in application No. 10-2016-7010619 Kazuki Yoshida et al ., “ Oxidative - Stability Enhancement and Charge Communication dated Aug. 24 , 2017 , from Korean Intellectual Transport Mechanism in Glyme - Lithium Salt Equimolar Com Property Office in application No. 10-2016-7010617 . plexes ” , Journal of the American Chemical Society, the U.S. , Kazuki Yoshida et al. , “ Oxidative - Stability Enhancement and Charge American Chemical Society, 2011 , No. 133 , p . 13121-13126 ( 9 Transport Mechanism in Glyme -Lithium Salt Equimolar Com pages ). plexes ” , Journal of the American Chemical Society, the U.S. , Notification of Reasons for Refusal dated Dec. 6 , 2018 , issued by American Chemical Society, 2011 , No. 133 , p . 13121-13129 ( 9 the Japanese Patent Office in JP 2015-172655 . pages ). Communication dated Jun . 10 , 2019 , issued by the U.S. Patent and Trademark Office in U.S. Appl. No. 15 / 024,418 . * cited by examiner U.S. Patent May 18 , 2021 Sheet 1 of 64 US 11,011,781 B2

Fig . 1

1 w 2250 ( cm )

Fig . 2

( cm - 1 ) U.S. Patent May 18 , 2021 Sheet 2 of 64 US 11,011,781 B2

Fig . 3

M 0.02

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Fig . 5

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( cm ) U.S. Patent May 18 , 2021 Sheet 4 of 64 US 11,011,781 B2

Fig . 7

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Fig . 8

Acetonitrile

( om ) U.S. Patent May 18 , 2021 Sheet 5 of 64 US 11,011,781 B2

Fig . 9

LiTFSA

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Fig . 10 LiFSA

2300 2150 ( cm - 1 ) U.S. Patent May 18 , 2021 Sheet 6 of 64 US 11,011,781 B2

Fig . 11

E11

0.1

( cm - 1 )

Fig . 12

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Fig . 13

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( cm - )

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( cm - 1 ) U.S. Patent May 18 , 2021 Sheet 8 of 64 US 11,011,781 B2

Fig . 15

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( cm - 1 ). U.S. Patent May 18 , 2021 Sheet 13 of 64 US 11,011,781 B2

Fig . 25

Dimethyl carbonate

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0.3

( cm - 1 ) U.S. Patent May 18 , 2021 Sheet 14 of 64 US 11,011,781 B2

Fig . 27 Diethyl carbonate

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( cm - ) U.S. Patent May 18 , 2021 Sheet 15 of 64 US 11,011,781 B2 Fig . 29

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( cm ) U.S. Patent May 18 , 2021 Sheet 16 of 64 US 11,011,781 B2 Fig . 31

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Fig . 37

2 Current/MA moet

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mACurrent/

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16 +

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100 150 200 250 300 350 400 --2 Temperature ( ° C )

Fig . 47

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2 A *

0 200 250 350 Temperature (° C ) U.S. Patent May 18 , 2021 Sheet 25 of 64 US 11,011,781 B2 Fig . 48

3 (StandardizedwithCapacityat0.1C) Example 1-1 6 3 ? Comparative Chargingcapacity } } } } Example 1-1 }

X 0.2 ?? 3 0 5 Cycle number

Fig . 49

2 Ist Charging maison 1st Discharging

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Capacity mAh / g U.S. Patent May 18 , 2021 Sheet 26 of 64 US 11,011,781 B2 Fig . 50

? 1st Charging * 1st Discharging .Xudde * 2nd Charging PotentialV - - 2nd Discharging one * 3rd Charging How w 3rd Discharging

Capacity mAh / g

Fig . 51

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Capacity mAh / g U.S. Patent May 18, 2021 Sheet 27 of 64 US 11,011,781 B2 Fig . 52

maman . Ist Charging Ist Discharging 2nd Charging Potentialv swww ww 2nd Discharging *** - 3rd Charging * * * 3rd Discharging

Capacity mAh / g

Fig . 53

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Capacity mAh / g U.S. Patent May 18 , 2021 Sheet 28 of 64 US 11,011,781 B2 Fig . 54 Example 1-12 0.3 5.0 M LiFSA / AN

0.2 VVoltage/

C /50 0.0 0 50 100 150 200 250 300 350 400 Capacity / mAh gh Fig . 55 Comparative Example 1-4 0.3 1.0 M LIPF / EC : DMC ( 1 : 1 )

? VVoltage/

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Fig . 56

0.3

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Comparative Example 2-1 VoltageV)( Example 2-1

Capacity ( mAh / g )

Fig . 58

1.20

XXX 0.50 retentionCapacityrateStandardized(withCurrentCapacityat0.1C)

* : Example 2-1 : Comparative Example 2-1 0.20

20 25 Cycle number U.S. Patent May 18, 2021 Sheet 31 of 64 US 11,011,781 B2 Fig . 59

2 1.8 1.6 1.4 Comparative Example 3-2 V)Voltage( 1.2 1 Example 3-2 0.8 0.6 0.4 0.2

0 500 1000 1500 Capacity ( mAh / g ) Example 3-2 ; ( Si - C complex : graphite : PAI = 75:15:10 ) Comparative Example 3-2 : ( Si - C complex : graphite : PAI = 75:15:10 )

Fig. 60

2 1.8 1.6 1,4 )Voltage(V 1.2

0.8 0.6 0,4 0.2

200 400 500 800 1000 1200 Capacity ( mAh / g ) U.S. Patent May 18, 2021 Sheet 32 of 64 US 11,011,781 B2 Fig . 61 Example 4-1 ( 4.5M LFSA I AN ) 2 1.9 1.8 1.7 Voltage)(V 1.6 1.5 1.4 1.3 1.2

1 0 50 100 150 Capacity ( mAh / g )

Fig . 62

Comparative Example 4-1 2 1.9 1.8 1.7 Voltage(V) 1.6 1.5 1.4 1.3 1.2 1.1 1 0 50 100 150 Capacity ( mAh / g ) U.S. Patent May 18, 2021 Sheet 33 of 64 US 11,011,781 B2 Fig . 63

2.8

2.6 1. 2.4 vsLi)VoltageV( 2.2 2 1.8

1.6 1,4 1.2

1 0 50 100 150 200 Charging / Discharging Capacity ( mAh / g )

Fig . 64

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1.2

50 150 200 Charging / Discharging Capacity ( mAh / g ) U.S. Patent May 18 , 2021 Sheet 34 of 64 US 11,011,781 B2

Fig . 65

Capacity retention rate ( Square root of cycles ) Example 5-2 110 % Comparative %)retentionrate(Capacity Example 5-3 80 %

i 30 % $ 8 20 22 24 Square root of cycle number U.S. Patent May 18 , 2021 Sheet 35 of 64 US 11,011,781 B2

Fig . 66

4500

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2000

1500

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Fig . 67

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Fig . 69

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Fig . 71

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50 150 200 250 300 350 400 Temperature ( ° C ) US 11,011,781 B2 1 2 NONAQUEOUS ELECTROLYTE Non -Patent Literature 3 : Y. Yamada et al . , Langmuir, 25 , SECONDARY BATTERY 12766-12770 ( 2009 ) . CROSS REFERENCE TO RELATED SUMMARY OF INVENTION APPLICATIONS 5 Technical Problem This application is a National Stage of International Application No. PCT/ JP2014 / 004911 filed Sep. 25 , 2014 , The present invention has been made in view of the above claiming priority based on Japanese Patent Application Nos . described circumstances, and a main problem to be solved 2013-198282, 2013-198283 , 2013-198284 , 2013-198285 , 10 by the present invention is to seek improvement of battery and 2013-198599 filed Sep. 25 , 2013 , 2014-065817 and characteristics by an optimum combination of an electrolytic 2014-065799 filed Mar. 27 , 2014 , 2014-186338 , 2014- solution and a negative electrode active material. 186339 , 2014-186340 , 2014-186341 and 2014-186342 filed Sep. 12 , 2014 , the contents of all of which are incorporated Solution to Problem herein by reference in their entirety . 15 Hereinafter, if necessary , “ an electrolytic solution con TECHNICAL FIELD taining a salt whose cation is an alkali metal , an alkaline The present invention relates to a nonaqueous electrolyte earth metal , or aluminum , and an organic solvent having a secondary battery such as a lithium ion secondary battery. 20 heteroelementpeak derived, fromand satisfyingthe organic , regarding solvent anin intensitya vibrational of a spectroscopy spectrum , Is > Io when an intensity of an origi BACKGROUND ART nal peak of the organic solvent is represented as lo and an For example, lithium ion secondary batteries are second intensity of a peak resulting from shifting of the original ary batteries capable of having a high charge / discharge 25 peak is represented as Is ” is sometimes referred to as “ an capacity and achieving high output. Currently, lithium ion electrolytic solution of the present invention .” secondary batteries are mainly used as power supplies for A feature of a nonaqueous electrolyte secondary battery portable electronic equipment, notebook personal comput- ( 1 ) of the present invention solving the above described ers , and electric vehicles . Thus, a secondary battery that is problem is including: the electrolytic solution of the present smaller and lighter has been demanded . In particular, for use 30 invention ; and a negative electrode having a negative elec in automobiles, since charging and discharging with large trode active material layer including a graphite whose G / D current have to be conducted, development of a secondary ratio , which is a ratio of G - band and D -band peaks in a battery having high rate characteristics capable of high- Raman spectrum , is not lower than 3.5 . In the present speed charging /discharging is demanded . invention , “ G / D ratio is not lower than 3.5 ” refers to either Lithium ion secondary batteries have, respectively on a 35 an area ratio or a height ratio of G -band and D - band peaks positive electrode and a negative electrode , active materials in a Raman spectrum being not lower than 3.5 , and particu capable of inserting and eliminating lithium ( Li ) therein / larly refers to a height ratio of said peaks being not lower therefrom . The batteries operate when lithium ions move than 3.5 . through an electrolytic solution sealed between the two A feature of a nonaqueous electrolyte secondary battery electrodes . In order to achieve high rate , improvement of 40 ( 2 ) of the present invention solving the above described binders and active materials used in the positive electrode problem is including: the electrolytic solution of the present and / or the negative electrode and improvement in the elec invention; and a negative electrode having a negative elec trolytic solution are necessary. trode active material layer that includes a carbon material secondaryAs a negative batteries electrode, carbon activematerials material such foras graphitelithium ionare 45 whose crystallite size, calculated from a half width of a peak widely used . In order to enable reversible insertion and appearing at 20 = 20 degrees to 30 degrees in a X - ray elimination of lithium ions with respect to the negative diffraction profile measured by X - ray diffraction method , is electrode active material , nonaqueous carbonate based sol- not larger than 20 nm . vents such as cyclic esters and linear esters are used in the A feature of a nonaqueous electrolyte secondary battery electrolytic solution . However, significant improvement in 50 ( 3 ) of the present invention solving the above described rate characteristics has been considered difficult when a problem is including: the electrolytic solution of the present carbonate based solvent is used . More specifically, as invention ; and a negative electrode including a negative described in Non - Patent Literature 1 to 3 , with a carbonate electrode active material that includes silicon element and / or based solvent such as ethylene carbonate and propylene tin element. carbonate, activation barrier of electrode reaction is large, 55 A feature of a nonaqueous electrolyte secondary battery and a fundamental review of the composition of the solvent ( 4 ) of the present invention solving the above described in the electrolytic solution has been considered necessary for problem is including: the electrolytic solution of the present improving rate characteristics. invention ; and a negative electrode including , as a negative electrode active material , a metal oxide configured to CITATION LIST 60 occlude and release lithium ions . A feature of a nonaqueous electrolyte secondary battery Non - Patent Literature ( 5 ) of the present invention solving the above described problem is including: the electrolytic solution of the present Non - Patent Literature 1 : T. Abe et al . , J. Electrochem . Soc . , invention ; and a negative electrode having a negative elec 151 , A1120 - A1123 ( 2004 ) . 65 trode active material layer that includes a graphite whose Non - Patent Literature 2 : T. Abe et al . , J. Electrochem . Soc . , ratio ( long axis / short axis ) of long axis to short axis is 1 to 152 , A2151 - A2154 ( 2005 ) . 5 . US 11,011,781 B2 3 4 Advantageous Effects of Invention FIG . 44 is a graph showing cyclic voltammetry ( CV ) of a nonaqueous electrolyte secondary battery of Comparative With the nonaqueous electrolyte secondary battery of the Example 1-6 ; present invention , battery characteristics improve. FIG . 45 is a graph showing cyclic voltammetry ( CV ) of 5 a nonaqueous electrolyte secondary battery of Comparative BRIEF DESCRIPTION OF DRAWINGS Example 1-7 ; FIG . 46 is a DSC chart of nonaqueous electrolyte sec FIG . 1 is an IR spectrum of electrolytic solution E3 ; ondary batteries of Example 1-5 and Comparative Example FIG . 2 is an IR spectrum of electrolytic solution E4 ; 1-8 ; FIG . 3 is an IR spectrum of electrolytic solution E7 ; 10 FIG . 47 is a DSC chart of nonaqueous electrolyte sec FIG . 4 is an IR spectrum of electrolytic solution E8 ; ondary batteries of Example 1-6 and Comparative Example FIG . 5 is an IR spectrum of electrolytic solution E10 ; 1-8 ; FIG . 6 is an IR spectrum of electrolytic solution C2 ; FIG . 48 is a graph showing the relationship between cycle FIG . 7 is an IR spectrum of electrolytic solution C4 ; number and current capacity ratio in the nonaqueous elec FIG . 8 is an IR spectrum of acetonitrile ; 15 trolyte secondary batteries of Example 1-1 and Comparative FIG . 9 is an IR spectrum of ( CF2SO2 ) 2NLi ; Example 1-1 ; FIG . 10 is an IR spectrum of ( FSO2 ) 2NLi ( 2100 to 2400 FIG . 49 shows charging / discharging curves of the non cm- ) ; aqueous electrolyte secondary battery of Example 1-8 ; FIG . 11 is an IR spectrum of electrolytic solution E11 ; 20 FIG . 50 shows charging / discharging curves of a nonaque FIG . 12 is an IR spectrum of electrolytic solution E12 ; ous electrolyte secondary battery of Example 1-9 ; FIG . 13 is an IR spectrum of electrolytic solution E13 ; FIG . 51 shows charging / discharging curves of a nonaque FIG . 14 is an IR spectrum of electrolytic solution E14 ; ous electrolyte secondary battery of Example 1-10 ; FIG . 15 is an IR spectrum of electrolytic solution E15 ; FIG . 52 shows charging / discharging curves of a nonaque FIG . 16 is an IR spectrum of electrolytic solution E16 ; 25 ous electrolyte secondary battery of Example 1-11 ; FIG . 17 is an IR spectrum of electrolytic solution E17 ; FIG . 53 shows charging / discharging curves of a nonaque FIG . 18 is an IR spectrum of electrolytic solution E18 ; ous electrolyte secondary battery of Comparative Example FIG . 19 is an IR spectrum of electrolytic solution E19 ; 1-9; FIG . 20 is an IR spectrum of electrolytic solution E20 ; FIG . 54 is a graph representing the relationship between FIG . 21 is an IR spectrum of electrolytic solution E21 ; 30 current rate and voltage curve in a nonaqueous electrolyte FIG . 22 is an IR spectrum of electrolytic solution C6 ; secondary battery of Example 1-12 ; FIG . 23 is an IR spectrum of electrolytic solution C7 ; FIG . 55 is a graph representing the relationship between FIG . 24 is an IR spectrum of electrolytic solution C8 ; current rate and voltage curve in a nonaqueous electrolyte FIG . 25 is an IR spectrum of dimethyl carbonate ; secondary battery of Comparative Example 1-4 ; FIG . 26 is an IR spectrum of ethyl methyl carbonate ; 35 FIG . 56 shows the results of cycle characteristics of FIG . 27 is an IR spectrum of diethyl carbonate ; Evaluation Example 19 ; FIG . 28 is an IR spectrum of ( FSO2 ) 2NLi ( 1900 to 1600 FIG . 57 shows initial charging /discharging curves of cm - 1) ; nonaqueous electrolyte secondary batteries of Example 2-1 FIG . 29 is a Raman spectrum of electrolytic solution E8 ; 40 and Comparative Example 2-1 ; FIG . 30 is a Raman spectrum of electrolytic solution E9 ; FIG . 58 is a graph representing the relationship between FIG . 31 is a Raman spectrum of electrolytic solution C4 ; cycle number and current capacity ratio in the nonaqueous FIG . 32 is a Raman spectrum of electrolytic solution E11 ; electrolyte secondary batteries of Example 2-1 and Com FIG . 33 is a Raman spectrum of electrolytic solution E13 ; parative Example 2-1 ; FIG . 34 is a Raman spectrum of electrolytic solution E15 ; 45 FIG . 59 shows charging /discharging curves of nonaque FIG . 35 is a Raman spectrum of electrolytic solution C6 ; ous electrolyte secondary batteries of Example 3-2 and FIG . 36 is a graph showing cyclic voltammetry ( CV ) of Comparative Example 3-2 ; a nonaqueous electrolyte secondary battery of Example 1-1 ; FIG . 60 shows charging / discharging curves of a nonaque FIG . 37 is a graph showing cyclic voltammetry ( CV ) of ous electrolyte secondary battery of Example 3-3 ; a nonaqueous electrolyte secondary battery of Example 1-2 ; 50 FIG . 61 shows charging / discharging curves of a nonaque FIG . 38 is a graph showing cyclic voltammetry ( CV ) of ous electrolyte secondary battery of Example 4-1 ; a nonaqueous electrolyte secondary battery of Example 1-3 ; FIG . 62 shows charging / discharging curves of a nonaque FIG . 39 is a graph showing cyclic voltammetry ( CV ) of ous electrolyte secondary battery of Comparative Example a nonaqueous electrolyte secondary battery of Comparative 4-1 ; Example 1-1 ; 55 FIG . 63 shows charging /discharging curves of a nonaque FIG . 40 is a graph showing cyclic voltammetry ( CV ) of ous electrolyte secondary battery of Example 4-2 ; a nonaqueous electrolyte secondary battery of Comparative FIG . 64 shows charging / discharging curves of a nonaque Example 1-2 ; ous electrolyte secondary battery of Example 4-3 ; FIG . 41 is a graph showing cyclic voltammetry ( CV ) of FIG . 65 is a graph showing the relationship between the a nonaqueous electrolyte secondary battery of Comparative 60 square root of cycle number and discharge capacity retention Example 1-3 ; rate when a cycle test was performed ; FIG . 42 is a graph showing cyclic voltammetry ( CV ) of FIG . 66 shows the results of XPS analysis of carbon a nonaqueous electrolyte secondary battery of Comparative element in negative - electrode S , O - containing coatings of Example 1-4 ; EB1 , EB2 , and CB1 in Evaluation Example 26 ; FIG . 43 is a graph showing cyclic voltammetry ( CV ) of 65 FIG . 67 shows the results of XPS analysis of fluorine a nonaqueous electrolyte secondary battery of Comparative element in the negative - electrode S , O - containing coatings of Example 1-5 ; EB1 , EB2 , and CB1 in Evaluation Example 26 ; US 11,011,781 B2 5 6 FIG . 68 shows the results of XPS analysis of nitrogen FIG . 90 is a graph showing the relationship between element in negative - electrode S , O - containing coatings of current and electrode potential in EB12 in Evaluation EB1 , EB2 , and CB1 in Evaluation Example 26 ; Example 36 ; FIG . 69 shows the results of XPS analysis of oxygen FIG . 91 is a graph showing the relationship between element in negative -electrode S , O -containing coatings of 5 potential ( 3.1 to 4.6 V ) and response current in EB12 in EB1 , EB2 , and CB1 in Evaluation Example 26 ; Evaluation Example 37 ; FIG . 70 shows the results of XPS analysis of sulfur FIG . 92 is a graph showing the relationship between element in the negative - electrode S , O - containing coatings of potential ( 3.1 to 5.1 V ) and response current in EB12 in EB1 , EB2 , and CB1 in Evaluation Example 26 ; Evaluation Example 37 ; 10 FIG . 93 is a graph showing the relationship between FIG . 71 shows the result of XPS analysis on the negative potential ( 3.1 to 4.6 V ) and response current in EB13 in electrode S , O - containing coating of EB1 in Evaluation Evaluation Example 37 ; Example 26 ; FIG . 94 is a graph showing the relationship between FIG . 72 shows the result of XPS analysis on the negative potential ( 3.1 to 5.1 V ) and response current in EB13 in electrode S , O - containing coating of EB2 in Evaluation 15 Evaluation Example 37 ; Example 26 ; FIG . 95 is a graph showing the relationship between FIG . 73 is a BF - STEM image of the negative - electrode potential ( 3.1 to 4.6 V ) and response current in EB14 in S , O - containing coating of EB1 in Evaluation Example 26 ; Evaluation Example 37 ; FIG . 74 shows the result of STEM analysis of C in the FIG . 96 is a graph showing the relationship between negative - electrode S , O - containing coating of EB1 in Evalu- 20 potential ( 3.1 to 5.1 V ) and response current in EB14 in ation Example 26 ; Evaluation Example 37 ; FIG . 75 shows the result of STEM analysis of O in the FIG . 97 is a graph showing the relationship between negative - electrode S , O -containing coating of EB1 in Evalu potential ( 3.1 to 4.6 V ) and response current in EB15 in ation Example 26 ; Evaluation Example 37 ; FIG . 76 shows the result of STEM analysis of S in the 25 FIG . 98 is a graph showing the relationship between negative - electrode S , O - containing coating of EB1 in Evalu potential ( 3.1 to 5.1 V ) and response current in EB15 in ation Example 26 ; Evaluation Example 37 ; FIG . 77 shows the result of XPS analysis of 0 in a FIG . 99 is a graph showing the relationship between positive - electrode S , O - containing coating of EB1 in Evalu potential ( 3.1 to 4.6 V ) and response current in CB6 in ation Example 26 ; 30 Evaluation Example 37 ; FIG . 78 shows the result of XPS analysis of S in the FIG . 100 is a graph showing the relationship between positive -electrode S , O - containing coating of EB1 in Evalu- potential ( 3.0 to 4.5 V ) and response current in EB13 in ation Example 26 ; Evaluation Example 37 , and is obtained by changing the FIG . 79 shows the result of XPS analysis of S in a scale of the vertical axis in FIG . 93 ; positive -electrode S , O - containing coating of EB4 in Evalu- 35 FIG . 101 is a graph showing the relationship between ation Example 26 ; potential ( 3.0 to 5.0 V ) and response current in EB13 in FIG . 80 shows the result of XPS analysis of O in the Evaluation Example 37 , and is obtained by changing the positive - electrode S , O - containing coating of EB4 in Evalu- scale of the vertical axis in FIG . 94 ; ation Example 26 ; FIG . 102 is a graph showing the relationship between FIG . 81 shows the results of XPS analysis of S in 40 potential ( 3.0 to 4.5 V ) and response current in EB16 in positive - electrode S , O - containing coatings of EB4 , EB5 , Evaluation Example 37 ; and CB2 in Evaluation Example 26 ; FIG . 103 is a graph showing the relationship between FIG . 82 shows the results of XPS analysis of S in potential ( 3.0 to 5.0 V ) and response current in EB16 in positive - electrode S , O -containing coatings of EB6 , EB7 , Evaluation Example 37 ; and CB3 in Evaluation Example 26 ; 45 FIG . 104 is a graph showing the relationship between FIG . 83 shows the results of XPS analysis of O in the potential ( 3.0 to 4.5 V ) and response current in CB7 in positive - electrode S , O -containing coatings of EB4 , EB5 , Evaluation Example 37 ; and CB2 in Evaluation Example 26 ; FIG . 105 is a graph showing the relationship between FIG . 84 shows the results of analysis of O in the positive- potential ( 3.0 to 5.0 V ) and response current in CB7 in electrode S , O - containing coatings of EB6 , EB7 , and CB3 in 50 Evaluation Example 37 ; Evaluation Example 26 ; FIG . 106 shows a DSC chart of EB19 in Evaluation FIG . 85 shows the results of analysis of Sin negative- Example 39 ; and electrode S , O - containing coatings of EB4 , EB5 , and CB2 in FIG . 107 shows a DSC chart of CB10 in Evaluation Evaluation Example 26 ; Example 39 . FIG . 86 shows the results of analysis of Sin negative- 55 electrode S , O - containing coatings of EB6 , EB7 , and CB3 in DESCRIPTION OF EMBODIMENTS Evaluation Example 26 ; FIG . 87 shows the results of analysis of O in the negative- The following describes embodiments of the present electrode S , O - containing coatings of EB4 , EB5 , and CB2 in invention . Unless mentioned otherwise in particular, a Evaluation Example 26 ; 60 numerical value range of “ a to b ” described in the present FIG . 88 shows the results of analysis of O in the negative- application includes , in the range thereof, a lower limit “ a ” electrode S , O - containing coatings of EB6 , EB7 , and CB3 in and an upper limit “ b .” A numerical value range can be Evaluation Example 26 ; formed by arbitrarily combining such upper limit values , FIG . 89 is a planar plot of complex impedance of batter- lower limit values , and numerical values described in ies , obtained by measuring alternating current impedances 65 Examples. In addition , numerical values arbitrarily selected after the first charging and discharging and after 100 cycles , within the numerical value range can be used as upper limit using EB8, EB9 , EB10 , and CB4 ; and lower limit numerical values . US 11,011,781 B2 7 8 The nonaqueous electrolyte secondary battery of the synergy between an effect derived from the negative elec present invention seeks improvement of battery character- trode active material and an effect derived from the electro istics by an optimum combination of an electrolytic solution lytic solution . and a negative electrode active material. Thus, no particular A main problem to be solved by the nonaqueous electro limitation exists for other battery components such as , for 5 lyte secondary battery ( 4 ) of the present invention is to example, positive electrodes . In addition , no particular limi- provide a nonaqueous electrolyte secondary battery that has tation exists also for charge carriers in the nonaqueous excellent energy density and charging /discharging efficiency electrolyte secondary battery of the present invention . For by using a metal oxide as a negative electrode active example , the nonaqueous electrolyte secondary battery of material . For example, as disclosed in JP2012160345 ( A ), the present invention may be a nonaqueous electrolyte 10 technologies using a metal oxide configured to occlude and secondary battery whose charge carrier is lithium ( e.g. , a release lithium ions as a negative electrode active material lithium secondary battery, a lithium ion secondary battery ), for a nonaqueous electrolyte secondary battery are known. or a nonaqueous electrolyte secondary battery whose charge As a type of such a metal oxide , for example, lithium titanate carrier is sodium ( e.g. , a sodium secondary battery, a sodium is known . In a nonaqueous electrolyte secondary battery ion secondary battery ). 15 whose negative electrode is lithium titanate, reactions for A main problem to be solved by the nonaqueous electro- occluding and releasing lithium are thought to occur stably, lyte secondary battery ( 1 ) of the present invention is to seek and , as a result , degradation of an active material is thought improvement of rate capacity characteristics and improve- to be suppressed . Thus , a nonaqueous electrolyte secondary ment of cycle characteristics by an optimum combination of battery having this type of metal oxide as the negative the electrolytic solution and the negative electrode active 20 electrode active material is known to have excellent cycle material. The nonaqueous electrolyte secondary battery ( 1 ) characteristics . On the other hand, the nonaqueous electro of the present invention includes the electrolytic solution of lyte secondary battery having this type of metal oxide as the the present invention , and a negative electrode having a negative electrode active material is known to have small negative electrode active material layer including a graphite energy density in the negative electrode when compared to whose G / D ratio , which is a ratio of G - band and D - band 25 a nonaqueous electrolyte secondary battery using a carbon peaks in a Raman spectrum , is not lower than 3.5 . The based negative electrode active material such as graphite . nonaqueous electrolyte secondary battery ( 1 ) of the present Thus, development of a nonaqueous electrolyte secondary invention as described above is a nonaqueous electrolyte battery that includes a metal oxide as the negative electrode secondary battery having improved rate capacity character- active material and has further improved battery character istics and cycle characteristics. When a graphite whose G / D 30 istics has been demanded . The nonaqueous electrolyte sec ratio is lower than 3.5 is used as the negative electrode active ondary battery ( 4 ) of the present invention uses a metal material, achieving both rate capacity and cycle character- oxide as the negative electrode active material and is excel istics is difficult even when the same electrolytic solution of lent in battery characteristics . the present invention is used . However, by using a graphite The nonaqueous electrolyte secondary battery ( 5 ) of the whose G / D ratio is not lower than 3.5 as the negative 35 present invention includes the electrolytic solution of the electrode active material, improvements in rate capacity present invention , and a negative electrode having a nega characteristics and also in cycle characteristics are achieved . tive electrode active material layer that includes a graphite A main problem to be solved by the nonaqueous electro- whose ratio ( long axis / short axis ) of long axis to short axis lyte secondary battery ( 2 ) of the present invention is to is 1 to 5. The nonaqueous electrolyte secondary battery ( 5 ) improve rate capacity characteristics by an optimum com- 40 of the present invention as described above is a nonaqueous bination of the electrolytic solution and the negative elec- electrolyte secondary battery having further improved input trode active material . The nonaqueous electrolyte secondary output characteristics . More specifically, when the electro battery ( 2 ) of the present invention includes the electrolytic lytic solution of the present invention is used , input - output solution of the present invention , and a negative electrode characteristics of a nonaqueous electrolyte secondary bat having a negative electrode active material layer that 45 tery improve . Furthermore , in addition to the electrolytic includes a carbon material whose crystallite size is not larger solution of the present invention, by using the graphite than 20 nm . The nonaqueous electrolyte secondary battery whose ratio ( long axis / short axis ) of long axis to short axis ( 2 ) of the present invention as described above can , by is 1 to 5 as the negative electrode active material, input including a carbon material satisfying 20 = 20 degrees to 30 output characteristics of a nonaqueous electrolyte secondary degrees as the negative electrode active material, achieve 50 battery are further improved . high rates compared to a nonaqueous electrolyte secondary < Electrolytic Solution > battery using a general electrolytic solution . The electrolytic solution of the present invention contains A main problem to be solved by the nonaqueous electro- a salt ( hereinafter, sometimes referred to as “ metal salt ” or lyte secondary battery ( 3 ) of the present invention is to seek simply “ salt ” ) whose cation is an alkali metal , an alkaline improvement of battery characteristics of a nonaqueous 55 earth metal , or aluminum , and an organic solvent having a electrolyte secondary battery by using silicon ( Si ) and tin heteroatom . Regarding an intensity of an original peak of the ( Sn ) as the negative electrode active material for the non- organic solvent in a vibrational spectroscopy spectrum , the aqueous electrolyte secondary battery. The nonaqueous elec- electrolytic solution satisfies Is > Io when an intensity of an trolyte secondary battery ( 3 ) of the present invention original peak of the organic solvent is represented as lo and includes the electrolytic solution of the present invention , 60 an intensity of a peak resulting from wave - number shifting and a negative electrode including silicon element and / or tin of the original peak of the organic solvent is represented as element in the negative electrode active material. When the Is . negative electrode active material including silicon and /or The relationship between Is and lo in a conventional tin , and carbon is used in combination with the electrolytic electrolytic solution is Is < lo . solution of the present invention ; the nonaqueous electrolyte 65 Metal Salt] secondary battery ( 3 ) of the present invention as described The metal salt may be a compound used as an electrolyte, above exerts excellent battery characteristics as a result of such as LiC104 , LiAsF6 , LIPF . , LiBF4 , and LiAlCl4 ordi US 11,011,781 B2 9 10 narily contained in an electrolytic solution of a battery . with a substituent group ; a heterocyclic group optionally Examples of a cation of the metal salt include alkali metals substituted with a substituent group ; an alkoxy group option such as lithium , sodium , and potassium , alkaline earth ally substituted with a substituent group ; an unsaturated metals such as beryllium , magnesium , calcium , strontium , alkoxy group optionally substituted with a substituent and barium , and aluminum . The cation of the metal salt is 5 group ; a thioalkoxy group optionally substituted with a preferably a metal ion identical to a charge carrier of the substituent group ; an unsaturated thioalkoxy group option battery in which the electrolytic solution is used . For ally substituted with a substituent group ; OH ; SH ; CN ; SCN ; example, when the electrolytic solution of the present inven or OCN . tion is to be used as an electrolytic solution for lithium ion In addition , R " , R " , Rº, and Rd each optionally bind with secondary batteries, the cation of the metal salt is preferably 10 Rl or R2 to form a ring .) lithium . The chemical structure of an anion of the salt may include R3X'Y General Formula ( 2 ) at least one element selected from a halogen , boron , nitro- ( R® is selected from : hydrogen ; a halogen ; an alkyl group gen , oxygen , sulfur, or carbon . Specific examples of the optionally substituted with a substituent group ; a cycloalkyl chemical structure of the anion including a halogen or boron 15 group optionally substituted with a substituent group ; an include : C104, PF , AsF , SbF , TaF , BF4 , SiF , B CH3 ) 4 unsaturated alkyl group optionally substituted with a sub Boxalate ) , Cl , Br, and I. stituent group ; an unsaturated cycloalkyl group optionally The chemical structure of the anion including nitrogen , substituted with a substituent group ; an aromatic group oxygen , sulfur, or carbon is described specifically in the optionally substituted with a substituent group ; a heterocy following 20 clic group optionally substituted with a substituent group ; an The chemical structure of the anion of the salt is prefer- alkoxy group optionally substituted with a substituent ably a chemical structure represented by the following group ; an unsaturated alkoxy group optionally substituted general formula ( 1 ) , general formula ( 2 ) , or general formula with a substituent group ; a thioalkoxy group optionally ( 3 ) . substituted with a substituent group ; an unsaturated thio 25 alkoxy group optionally substituted with a substituent ( R'X ) ( R2x2 ) N General Formula ( 1 ) group ; CN ; SCN ; or OCN . ( R ' is selected from : hydrogen ; a halogen ; an alkyl group X² is selected from SO2 , CFO , C = S , R?P = O , RP = S , optionally substituted with a substituent group ; a cycloalkyl S = O , or Si = O . group optionally substituted with a substituent group ; an R and R * are each independently selected from : hydro unsaturated alkyl group optionally substituted with a sub- 30 gen ; a halogen ; an alkyl group optionally substituted with a stituent group ; an unsaturated cycloalkyl group optionally substituent group ; a cycloalkyl group optionally substituted substituted with a substituent group ; an aromatic group with a substituent group; an unsaturated alkyl group option optionally substituted with a substituent group ; a heterocy- ally substituted with a substituent group ; an unsaturated clic group optionally substituted with a substituent group ; an cycloalkyl group optionally substituted with a substituent alkoxy group optionally substituted with a substituent 35 group ; an aromatic group optionally substituted with a group ; an unsaturated alkoxy group optionally substituted substituent group ; a heterocyclic group optionally substi with a substituent group ; a thioalkoxy group optionally tuted with a substituent group ; an alkoxy group optionally substituted with a substituent group ; an unsaturated thio- substituted with a substituent group ; an unsaturated alkoxy alkoxy group optionally substituted with a substituent group optionally substituted with a substituent group ; a group ; CN ; SCN ; or OCN . 40 thioalkoxy group optionally substituted with a substituent R2 is selected from : hydrogen; a halogen ; an alkyl group group; an unsaturated thioalkoxy group optionally substi optionally substituted with a substituent group ; a cycloalkyl tuted with a substituent group; OH ; SH ; CN ; SCN ; or OCN . group optionally substituted with a substituent group ; an In addition , R? and Rf each optionally bind with R? to form unsaturated alkyl group optionally substituted with a sub- a ring. stituent group ; an unsaturated cycloalkyl group optionally 45 Y is selected from O or S. ) substituted with a substituent group ; an aromatic group optionally substituted with a substituent group ; a heterocy (R4X4 ) ( R $ X $ ) (R®X® ) C General Formula ( 3 ) clic group optionally substituted with a substituent group ; an ( R4 is selected from : hydrogen ; a halogen ; an alkyl group alkoxy group optionally substituted with a substituent optionally substituted with a substituent group ; a cycloalkyl group ; an unsaturated alkoxy group optionally substituted 50 group optionally substituted with a substituent group ; an with a substituent group ; a thioalkoxy group optionally unsaturated alkyl group optionally substituted with a sub substituted with a substituent group ; an unsaturated thio- stituent group ; an unsaturated cycloalkyl group optionally alkoxy group optionally substituted with a substituent substituted with a substituent group ; an aromatic group group ; CN ; SCN ; or OCN . optionally substituted with a substituent group ; a heterocy Furthermore, R ' and R2 optionally bind with each other to 55 clic group optionally substituted with a substituent group ; an form a ring . alkoxy group optionally substituted with a substituent Xl is selected from SO2 , C = 0 , C = S , R?P = O , R ™ P = S , group ; an unsaturated alkoxy group optionally substituted S = 0 , or Si = O . with a substituent group ; a thioalkoxy group optionally X2 is selected from SO2 , CFO , C = S , RP = O , ROP = S, substituted with a substituent group ; an unsaturated thio S = 0 , or Si = O . 60 alkoxy group optionally substituted with a substituent R “, R " , Rº , and Rd are each independently selected from : group ; CN ; SCN ; or OCN . hydrogen ; a halogen ; an alkyl group optionally substituted R5 is selected from : hydrogen ; a halogen ; an alkyl group with a substituent group ; a cycloalkyl group optionally optionally substituted with a substituent group ; a cycloalkyl substituted with a substituent group ; an unsaturated alkyl group optionally substituted with a substituent group; an group optionally substituted with a substituent group ; an 65 unsaturated alkyl group optionally substituted with a sub unsaturated cycloalkyl group optionally substituted with a stituent group ; an unsaturated cycloalkyl group optionally substituent group ; an aromatic group optionally substituted substituted with a substituent group ; an aromatic group US 11,011,781 B2 11 12 optionally substituted with a substituent group ; a heterocy- group , sulfinyl group , ureido groups, phosphoric acid amide clic group optionally substituted with a substituent group ; an groups , sulfo group , carboxyl group , hydroxamic acid alkoxy group optionally substituted with a substituent groups , sulfino group , hydrazino group , imino group , and group ; an unsaturated alkoxy group optionally substituted silyl group , etc. These substituent groups may be further with a substituent group ; a thioalkoxy group optionally 5 substituted . In addition , when two or more substituent substituted with a substituent group ; an unsaturated thio- groups exist , the substituent groups may be identical or alkoxy group optionally substituted with a substituent different from each other . group ; CN ; SCN ; or OCN . The chemical structure of the anion of the salt is more Ro is selected from : hydrogen ; a halogen ; an alkyl group preferably a chemical structure represented by the following optionally substituted with a substituent group ; a cycloalkyl 10 general formula ( 4 ) , general formula ( 5 ) , or general formula group optionally substituted with a substituent group ; an ( 6 ) . unsaturated alkyl group optionally substituted with a sub stituent group ; an unsaturated cycloalkyl group optionally (R7x7 ) ( R $ X $ ) N General Formula ( 4 ) substituted with a substituent group ; an aromatic group ( R7 and R8 are each independently C „ H ,F , C1 Brd optionally substituted with a substituent group; a heterocy- 15 le ( CN ) ( SCN ) , (OCN ) n. clic group optionally substituted with a substituent group ; an “ n , ” “ a , " “ b ” “ c , " “ d , ” “ e , ” “ f , ” “ g , ” and “ h ” are each alkoxy group optionally substituted with a substituent independently an integer not smaller than 0 , and satisfy group ; an unsaturated alkoxy group optionally substituted 2n + 1 = a + b + c + d + e + f + g + h . with a substituent group ; a thioalkoxy group optionally In addition , R7 and R8 optionally bind with each other to substituted with a substituent group ; an unsaturated thio- 20 form a ring, and , in that case , satisfy 2n = a + b + c + d + e + f + g + h . alkoxy group optionally substituted with a substituent X ' is selected from SO2 , C = 0 , C = S , R ™ P = 0 , R ™ P = S , group ; CN ; SCN ; or OCN . S = O , or Si = O . In addition , any two or three of R4, R5 , and R optionally X® is selected from SO2 , C = O , C = S , R ° P = O , RPP = S , bind with each other to form a ring . S = O , or Si = O . X4 is selected from SO2 , CFO , C = S , R & P = 0 , R ™ P = S , 25 R " , R " , Rº , and RP are each independently selected from : S = 0 , or Si = O . hydrogen ; a halogen ; an alkyl group optionally substituted X is selected from SO ,, C = 0 , C = S , R'P = O , RP = S , with a substituent group ; a cycloalkyl group optionally S = O , or Si = O . substituted with a substituent group ; an unsaturated alkyl Xó is selected from SO2 , C = 0 , C = S , R'P = 0 , R'P = S , group optionally substituted with a substituent group ; an S = 0 , or Si = O . 30 unsaturated cycloalkyl group optionally substituted with a R8, R " , R ' , R ', R ", and R ’ are each independently selected substituent group ; an aromatic group optionally substituted from : hydrogen ; a halogen ; an alkyl group optionally sub with a substituent group ; a heterocyclic group optionally stituted with a substituent group ; a cycloalkyl group option substituted with a substituent group ; an alkoxy group option ally substituted with a substituent group ; an unsaturated ally substituted with a substituent group ; an unsaturated alkyl group optionally substituted with a substituent group ; 35 alkoxy group optionally substituted with a substituent an unsaturated cycloalkyl group optionally substituted with group ; a thioalkoxy group optionally substituted with a a substituent group ; an aromatic group optionally substituted substituent group ; an unsaturated thioalkoxy group option with a substituent group ; a heterocyclic group optionally ally substituted with a substituent group ; OH ; SH ; CN ; SCN ; substituted with a substituent group ; an alkoxy group option or OCN . ally substituted with a substituent group ; an unsaturated 40 In addition , R " , R " , Rº , and Rp each optionally bind with alkoxy group optionally substituted with a substituent R ? or R8 to form a ring .) group ; a thioalkoxy group optionally substituted with a Rºx9Y substituent group ; an unsaturated thioalkoxy group option General Formula ( 5 ) ally substituted with a substituent group ; OH ; SH ; CN ; SCN ; ( Rºis C , H , F , CI Br 1 (CN ) SCN ) (OCN )) or OCN . 45 " n ," " a , " " b , " " c , " " d ," " e , " " f ," " g ,” and “ h ” are each In addition , RS, R " , R ', R , R " , and R ' each optionally bind independently an integer not smaller than 0 , and satisfy with R4, RS , or R to form a ring . ) 2n + 1 = a + b + c + d + e + f + g + h . The wording of “ optionally substituted with a substituent X® is selected from SO2 , C = O , C S , R ? P = 0 , R'P = S , group ” in the chemical structures represented by the above S = 0 , or Si = 0 . described general formulae ( 1 ) to ( 3 ) is to be described . For 50 R9 and R ” are each independently selected from : hydro example , " an alkyl group optionally substituted with a gen ; a halogen ; an alkyl group optionally substituted with a substituent group ” refers to an alkyl group in which one or substituent group ; a cycloalkyl group optionally substituted more hydrogen atoms of the alkyl group is substituted with with a substituent group ; an unsaturated alkyl group option a substituent group , or an alkyl group not including any ally substituted with a substituent group ; an unsaturated particular substituent groups. 55 cycloalkyl group optionally substituted with a substituent Examples of the substituent group in the wording of group ; an aromatic group optionally substituted with a " optionally substituted with a substituent group ” include substituent group ; a heterocyclic group optionally substi alkyl groups , alkenyl groups , alkynyl groups, cycloalkyl tuted with a substituent group ; an alkoxy group optionally substituted with a substituent group ; an unsaturated alkoxy heterocyclicgroups, unsaturated groups, halogenscycloalkyl, OHgroups , SH , CNaromatic , SCN ,groups OCN ,, 60 group optionally substituted with a substituent group ; a nitro group , alkoxy groups , unsaturated alkoxy groups , thioalkoxy group optionally substituted with a substituent amino group , alkylamino groups , dialkylamino groups , ary group ; an unsaturated thioalkoxy group optionally substi loxy groups, acyl groups , alkoxycarbonyl groups , acyloxy tuted with a substituent group ; OH ; SH ; CN ; SCN ; or OCN . groups , aryloxycarbonyl groups , acyloxy groups , acylamino In addition , R9 and R ’ each optionally bind with Rº to groups, alkoxycarbonylamino groups , aryloxycarbo- 65 form a ring nylamino groups, sulfonylamino groups , sulfamoyl groups , Y is selected from O or S. ) carbamoyl group , alkylthio groups, arylthio groups, sulfonyl (R10x10 (Rllxll ) (R12x12 ) General Formula ( 6 ) US 11,011,781 B2 13 14 (Rº , R11 , and R12 are each independently “ n , ” “ a , ” “ b , ” “ c ,” “ d ,” and “ e ” are each independently an C , H , F , Cl_Br1 ( CN ), ( SCN ) (OCN ) integer not smaller than 0 , and satisfy 2n + 1 = a + b + c + d + e . “ n ,” “ a , ” “ b , " " c , " " d , " " e ,” “ f , ” “ g , ” and “ h ” are each Any two of R16 , R17 , and R18 optionally bind with each independently an integer not smaller than 0 , and satisfy other to form a ring , and , in that case , groups forming the 2n + 1 = a + b + c + d + e + f + g + h . 5 ring satisfy 2n = a + b + c + d + e . In addition , the three of R16 , Any two of R10 , R1 , and R12 optionally bind with each R ! ) , and R18 optionally bind with each other to form a ring , other to form a ring , and in that case , groups forming the ring and , among the three in that case , two groups satisfy satisfy 2n = a + b + c + d + e + f + g + h. In addition , the three of R10 , 2n = a + b + c + d + e and one group satisfies 2n - 1 = a + b + c + d + e . ) Rll , and R12 optionally bind with each other to form a ring, In the chemical structures represented by the general and , in that case , two groups satisfy 2n = a + b + c + d + e + f + g + h 10 formulae ( 7 ) to ( 9 ) , “ n ” is preferably an integer from 0 to 6 , and one group satisfies 2n - 1 = a + b + c + d + e + f + g + h . more preferably an integer from 0 to 4 , and particularly Xlº is selected from SO2 , CFO , CES , RSP = O , R?P = S , preferably an integer from 0 to 2. In the chemical structures S = 0 , or Si = O . represented by the general formulae ( 7 ) to ( 9 ) , when R13 and xll is selected from SO2 , C = 0 , C = S , R “ P = O , R'P = S , R14 bind with each other or R16 , R17 , and R18 bind with each S = O , or Si = O . 15 other to form a ring ; “ n ” is preferably an integer from 1 to Xl2 is selected from SO2 , C30 , CES , R ™ P = 0 , R ™ P = S , 8 , more preferably an integer from 1 to 7 , and particularly S = O , or Si = O . preferably an integer from 1 to 3 . R®, R " , R “ , R ' , R " , and R * are each independently selected In addition , in the chemical structures represented by the from : hydrogen ; a halogen ; an alkyl group optionally sub- general formulae ( 7 ) to ( 9 ) , those in which “ a , " " c , ” « d , ” and stituted with a substituent group ; a cycloalkyl group option- 20 “ e ” are 0 are preferable . ally substituted with a substituent group ; an unsaturated The metal salt is particularly preferably ( CF2SO2 ) 2NLI alkyl group optionally substituted with a substituent group ; ( hereinafter sometimes referred to as “ LiTFSA ” ), an unsaturated cycloalkyl group optionally substituted with ( F_02 ) 2NLi ( hereinafter sometimes referred to as “ LiFSA ” ), a substituent group ; an aromatic group optionally substituted (C2F SO2) 2NLI , FSO ( CF2SO2) NLi, (S02CF CF_S02 ) with a substituent group ; a heterocyclic group optionally 25 NLi , ( SO2CF2CF2CF2SO2 ) NLi , FSO2 ( CH2SO2 ) NLi , FSO2 substituted with a substituent group ; an alkoxy group option- ( C2F5S02 ) NLi , or FSO2( C2H SO2 ) NLi . ally substituted with a substituent group ; an unsaturated As the metal salt , one that is obtained by combining alkoxy group optionally substituted with a substituent appropriate numbers of an anion and a cation described group ; a thioalkoxy group optionally substituted with a above may be used . Regarding the metal salt , a single type substituent group ; an unsaturated thioalkoxy group option- 30 may be used , or a combination of multiple types may be ally substituted with a substituent group ; OH ; SH ; CN ; SCN ; used . or OCN . [ Organic Solvent] In addition, RS, R " , RU , RY , R " , and R * each optionally bind As the organic solvent having a heteroelement, an organic with R10 , R1, or R 12 to form a ring .) solvent whose heteroelement is at least one selected from In the chemical structures represented by the general 35 nitrogen , oxygen , sulfur, or a halogen is preferable, and an formulae ( 4 ) to ( 6 ) , the meaning of the wording of “ option- organic solvent whose heteroelement is at least one selected ally substituted with a substituent group ” is synonymous from nitrogen or oxygen is more preferable. In addition , as with that described for the general formulae ( 1 ) to ( 3 ) . the organic solvent having the heteroelement, an aprotic In the chemical structures represented by the general solvent not having a proton donor group such as NH group , formulae ( 4 ) to ( 6 ) , “ n ” is preferably an integer from 0 to 6 , 40 NH , group , OH group , and SH group is preferable . more preferably an integer from 0 to 4 , and particularly Specific examples of the organic solvent having the preferably an integer from 0 to 2. In the chemical structures heteroelement” ( hereinafter, sometimes simply referred to as represented by the general formulae ( 4 ) to ( 6 ) , when R7 and " organic solvent ” ) include nitriles such as acetonitrile, pro R8 bind with each other or R10 , R11 , and Rl2 bind with each pionitrile, acrylonitrile, and malononitrile , ethers such as other to form a ring; “ n ” is preferably an integer from 1 to 45 1,2 - dimethoxyethane, 1,2 - diethoxyethane, tetrahydrofuran , 8 , more preferably an integer from 1 to 7 , and particularly 1,2 - dioxane, 1,3 - dioxane, 1,4 - dioxane, 2,2 - dimethyl- 1,3 - di preferably an integer from 1 to 3 . oxolane , 2 -methyltetrahydropyran , 2 -methyltetrahydro The chemical structure of the anion of the salt is more furan , and crown ethers, carbonates such as ethylene car preferably one that is represented by the following general bonate , propylene carbonate, dimethyl carbonate, diethyl formula ( 7 ) , general formula ( 8 ) , or general formula ( 9 ) . 50 carbonate , and ethyl methyl carbonate , amides such as formamide, N , N - dimethylformamide, N , N -dimethylacet (R13502 ) R4802( ) N General Formula ( 7 ) amide , and N -methylpyrrolidone , isocyanates such as iso propyl isocyanate, n -propylisocyanate , and chloromethyl ( R13 and R 14 are each independently C , H , F , C1 Brje. isocyanate , esters such as methyl acetate , ethyl acetate , " n , ” “ a , " “ b ," " c , " " d , ” and “ e ” are each independently an 55 propyl acetate , methyl propionate , methyl formate , ethyl integer not smaller than 0 , and satisfy 2n + 1 = a + b + c + d + e . formate, vinyl acetate , methyl acrylate, and methyl meth In addition , R13 and R14 optionally bind with each other acrylate, epoxies such as glycidyl methyl ether, epoxy to form a ring, and , in that case , satisfy 2n = a + b + c + d + e . ) butane, and 2 - ethyloxirane, oxazoles such as oxazole , 2 - eth R15SO General Formula ( 8 ) yloxazole , oxazoline, and 2 -methyl - 2 -oxazoline , ketones ( R15 is C , H ,F , CI Br . 60 such as acetone , methyl ethyl ketone, and methyl isobutyl ?? ketone, acid anhydrides such as acetic anhydride and pro “ n ,” “ a , ” “ b , ” “ C , " “ d , ” and “ e ” are each independently an pionic anhydride, sulfones such as dimethyl sulfone and integer not smaller than 0 , and satisfy 2n + 1 = a + b + c + d + e . ) sulfolane, sulfoxides such as dimethyl sulfoxide , nitros such as 1 - nitropropane and 2 -nitropropane , furans such as furan ( R16SO2 ) ( R7S02 ) ( R18502 ) General Formula ( 9 ) 65 and furfural, cyclic esters such as y - butyrolactone , y -vale (R16 R17 , and R18 are each independently rolactone, and d - valerolactone, aromatic heterocycles such C „ H , F , Cl Brale as thiophene and pyridine , heterocycles such as tetrahydro US 11,011,781 B2 15 16 4 - pyrone, 1 -methylpyrrolidine , and N -methylmorpholine , and Io most easily . In addition , when multiple types of the and phosphoric acid esters such as trimethyl phosphate and organic solvent having the heteroelement are used in the triethyl phosphate . electrolytic solution of the present invention , an organic Examples of the organic solvent having a heteroelement solvent enabling determination of the relationship between include linear carbonates represented by the following gen- 5 Is and lo most easily ( resulting in the largest difference eral formula ( 10 ) . between Is and Io ) is selected , and the relationship between R1'OCOOR20 Is and Io may be determined based on the obtained peak General Formula ( 10 ) intensity. In addition , when the peak shift amount is small ( R19 and R20 are each independently selected from and peaks before and after shifting overlap with each other C „ H , F , C1 Brale that is a linear alkyl, or CmHF C1, Br; I ; 10 to give an appearance like a smooth mountain , the relation whose chemical structure includes a cyclic alkyl. “ n , ” “ a , ship between Is and Io may be determined by performing “ b , ” “ c , ” “ d , ” " e , ” “ m ,” “ f, " " g , ” “ h ,” “ ,” and “ j ” are each peak resolution with known means . independently an integer not smaller than 0 , and satisfy In the vibrational spectroscopy spectrum of the electro 2n In+ 1 =the a + blinear + c + d +carbonates e and 2m = representedf + g + h + i + j) by the general for- 15 lytic solution using multiple types of the organic solvent mula ( 10 ) , “ n ” is preferably an integer from 1 to 6 , more having the heteroelement, a peak of an organic solvent most preferably an integer from 1 to 4 , and particularly preferably easily coordinated with a cation ( hereinafter, sometimes an integer from 1 to 2. “ m ” is preferably an integer from 3 referred to as “ preferential coordination solvent ” ) shifts to 8 , more preferably an integer from 4 to 7 , and particularly preferentially from others . In the electrolytic solution using preferably an integer from 5 to 6. In addition , among the 20 multiple types of the organic solvent having the heteroele linear carbonates represented by the general formula ( 10 ) , ment, the mass % of the preferential coordination solvent dimethyl carbonate ( hereinafter, sometimes referred to as with respect to the whole organic solvent having the het “ DMC " ), diethyl carbonate ( hereinafter, sometimes referred eroelement is preferably 40 % or higher, more preferably to as “ DEC ” ), and ethyl methyl carbonate ( hereinafter, 50 % or higher, further preferably 60 % or higher, and par sometimes referred to as “ EMC ” ) are particularly preferable . 25 ticularly preferably 80 % or higher. In addition , in the As the organic solvent having a heteroelement, a solvent electrolytic solution using multiple types of the organic whose relative permittivity is not smaller than 20 or that has solvent having the heteroelement, the vol % of the prefer ether oxygen having donor property is preferable, and ential coordination solvent with respect to the whole organic examples of such an organic solvent include nitriles such as solvent having the heteroelement is preferably 40 % or acetonitrile, propionitrile , acrylonitrile, and malononitrile , 30 higher, more preferably 50 % or higher, further preferably ethers such as 1,2 - dimethoxyethane, 1,2 -diethoxyethane , 60 % or higher, and particularly preferably 80 % or higher. tetrahydrofuran , 1,2 - dioxane , 1,3 - dioxane, 1,4 -dioxane , 2,2- The relationship between the two peak intensities satisfies dimethyl - 1,3 - dioxolane, 2 methyltetrahydropyran- , 2 -meth- a condition of Is > 2xlo , further preferably satisfies a condi yltetrahydrofuran , and crown ethers , N , N -dimethylforma- tion of Is > 3xIo , and particularly preferably satisfies a con mide, acetone , dimethyl sulfoxide, and sulfolane . Among 35 dition of Is > 5xIo . A most preferable electrolytic solution is those , acetonitrile ( hereinafter, sometimes referred to as one in which the intensity lo of the original peak of the “ AN ” ) and 1,2 -dimethoxyethane (hereinafter , sometimes organic solvent is not observed and the intensity Is of the referred to as “ DME ” ) are particularly preferable . shift peak is observed in the vibrational spectroscopy spec Regarding these organic solvents, a single type may be trum of the electrolytic solution of the present invention . used by itself in the electrolytic solution , or a combination 40 This means that, in the electrolytic solution , all molecules of of two or more types may be used . the organic solvent contained in the electrolytic solution are A feature of the electrolytic solution of the present inven- completely solvated with the metal salt . The electrolytic tion is , in its vibrational spectroscopy spectrum and regard- solution of the present invention is most preferably in a state ing an intensity of a peak derived from the organic solvent in which all molecules of the organic solvent contained in contained in the electrolytic solution of the present inven- 45 the electrolytic solution are completely solvated with the tion , satisfying Is > Io when an intensity of an original peak metal salt ( a state of Io = 0 ) . of the organic solvent is represented as lo and an intensity In the electrolytic solution of the present invention , the of “ a peak resulting from shifting of the original peak of the metal salt and the organic solvent having the heteroelement organic solvent ” ( hereinafter, sometimes referred to as “ shift ( or the preferential coordination solvent) are estimated to peak ” ) is represented as Is . More specifically , in a vibrational 50 interact with each other. Specifically, the metal salt and the spectroscopy spectrum chart obtained by subjecting the heteroelement in the organic solvent having the heteroele electrolytic solution of the present invention to vibrational ment ( or the preferential coordination solvent) are estimated spectroscopy measurement, the relationship between the two to form a coordinate bond and form a stable cluster formed peak intensities is Is > Io . of the metal salt and the organic solvent having the hetero Here, “ an original peak of the organic solvent ” refers to a 55 element ( or the preferential coordination solvent ). Based on peak observed at a peak position (wave number) when the results from later described Examples , the cluster is esti vibrational spectroscopy measurement is performed only on mated to be formed mostly from coordination of 2 molecules the organic solvent. The value of the intensity lo of the of the organic solvent having the heteroelement ( or the original peak of the organic solvent and the value of the preferential coordination solvent) with respect to 1 molecule intensity Is of the shift peak are the heights or area sizes from 60 of the metal salt . When this point is taken into consideration , a baseline of respective peaks in the vibrational spectros- in the electrolytic solution of the present invention , the mol copy spectrum . range of the organic solvent having the heteroelement ( or the In the vibrational spectroscopy spectrum of the electro- preferential coordination solvent) with respect to 1 mol of lytic solution of the present invention , when multiple peaks the metal salt is preferably not lower than 1.4 mol but lower resulting from shifting of the original peak of the organic 65 than 3.5 mol , more preferably not lower than 1.5 mol but not solvent exist , the relationship may be determined based on higher than 3.1 mol , and further preferably not lower than a peak enabling determination of the relationship between Is 1.6 mol but not higher than 3 mol . US 11,011,781 B2 17 18 The viscosity n (mPa.s ) of the electrolytic solution of the environment and has a high density when compared to the present invention is preferably in a range of 10 < n < 500 , conventional electrolytic solution ; improvement in a metal more preferably in a range of 12 < n < 400 , further preferably ion transportation rate in the electrolytic solution ( particu in a range of 15 < n < 300 , particularly preferably in a range of larly improvement of lithium transference number when the 18 < n < 150, and most preferably in a range of 20 < n < 140. 5 metal is lithium ), improvement in reaction rate between an The electrolytic solution of the present invention displays excellent ionic conductivity . Thus, the nonaqueous electro electrode and an electrolytic solution interface , mitigation of lyte secondary battery of the present invention has excellent uneven distribution of salt concentration in the electrolytic battery characteristics . An ionic conductivity o (mS / cm ) of solution caused when a battery undergoes high - rate charge the electrolytic solution of the present invention preferably 10 doubleand discharge layer is, andexpected increase. In inthe the electrolytic capacity solutionof an electrical of the satisfies 1so . present invention , since the density is high , the vapor When the ionic conductivity o (mS / cm ) of the electrolytic pressure of the organic solvent contained in the electrolytic solution of the present invention is higher, ions can move solution becomes low . As a result , volatilization of the cansuitably be obtained and an .excellent Regarding electrolytic the ionic solutionconductivity of a batteryo (m5 / 15 organic solvent from the electrolytic solution of the present cm ) of the electrolytic solution of the present invention , if a invention is reduced . suitable range including an upper limit is to be shown , a In the electrolytic solution of the present invention , since range of 2 < o < 200 is preferable, a range of 3 < o < 100 is more a cluster is estimated to be formed mostly from coordination preferable , a range of 4 < o < 50 is further preferable , and a of 2 molecules of the organic solvent having the heteroele range of 5 < o < 35 is particularly preferable. 20 ment ( or the preferential coordination solvent) with respect A density d ( g / cm ) of the electrolytic solution of the to 1 molecule of the metal salt , the concentration ( mol / L ) of present invention preferably satisfies d21.2 or d22.2 , and is the electrolytic solution of the present invention depends on preferably within a range of 1.25d52.2 , more preferably respective molecular weights of the metal salt and the within a range of 1.24sds2.0 , further preferably within a organic solvent, and the density in the solution . Thus, range of 1.26sds1.8 , and particularly preferably within a 25 unconditionally defining the concentration of the electrolytic range of 1.27sds1.6 . The density d ( g / cm ) of the electro- solution of the present invention is not appropriate . lytic solution of the present invention refers to the density at 20 ° C. " d / c ” described in the following is a value obtained Concentration (mol / L ) of each of the electrolytic solutions by dividing “ d ” described above by a salt concentration c of the present invention is shown in Table 1 . (mol / L ). 30 In the electrolytic solution of the present invention , d / c is TABLE 1 within a range of 0.15sd /cs0.71 , more preferably within a Metal salt Organic solvent Concentration (mol / L ) range of 0.15sd / cs0.56 , even more preferably within a range LiTFSA DME 2.2 to 3.4 of 0.25sd /cs0.56 , further preferably within a range of 0.2sd / LiTFSA AN 3.2 to 4.9 c50.50 , and particularly preferably within a range of 0.27sd / 35 LiFSA DME 2.6 to 4.1 c < 0.47 . LiFSA AN 3.9 to 6.0 LiFSA DMC 2.3 to 4.5 “ d / c ” of the electrolytic solution of the present invention LiFSA EMC 2.0 to 3.8 is defined also when the metal salt and the organic solvent LiFSA 1.8 to 3.6 are specified . For example, when LiTFSA and DME are DEC respectively selected as the metal salt and the organic 40 solvent, d / c is preferably within a range of 0.42sd / cs0.56 An organic solvent forming the cluster and an organic and more preferably within a range of 0.4sd / cs0.52 . When solvent not involved in the formation of the cluster are LiTFSA and AN are respectively selected as the metal salt different in terms of the environment in which the respective and the organic solvent, d / c is preferably within a range of organic solvents exist. Thus, in the vibrational spectroscopy 0.35sd /cs0.41 and more preferably within a range of 45 measurement, a peak derived from the organic solvent 0.365d / cs0.39 . When LiFSA and DME are respectively forming the cluster is observed to be shifted toward the high selected as the metal salt and the organic solvent, d / c is wave number side or the low wave number side with respect preferably within a range of 0.32sd / cs0.46 and more pref- to the wave number observed at a peak ( original peak of the erably within a range of 0.34sd / cs0.42 . When LiFSA and organic solvent) derived from the organic solvent not AN are respectively selected as the metal salt and the 50 involved in the formation of the cluster. Thus, the shift peak organic solvent, d / c is preferably within a range of 0.25sd / represents a peak of the organic solvent forming the cluster . c50.48 , more preferably within a range of 0.25sd / c 0.38 , Examples of the vibrational spectroscopy spectrum further preferably within a range of 0.25sd /cs0.31 , and even include an IR spectrum or a Raman spectrum . Examples of further preferably within a range of 0.2sd / cs0.29 . When measuring methods of IR measurement include transmission LiFSA and DMC are respectively selected as the metal salt 55 measuring methods such as Nujol mull method and liquid and the organic solvent, d / c is preferably within a range of film method , and reflection measuring methods such as ATR 0.32sd / cs0.46 and more preferably within a range of method. Regarding which of the IR spectrum and the Raman 0.34sd /cs0.42 . When LiFSA and EMC are respectively spectrum is to be selected , a spectrum enabling easy deter selected as the metal salt and the organic solvent, d / c is mination of the relationship between Is and Io may be preferably within a range of 0.34sd / cs0.50 and more pref- 60 selected as the vibrational spectroscopy spectrum of the erably within a range of 0.37sd / cs0.45 . When LiFSA and electrolytic solution of the present invention . The vibrational DEC are respectively selected as the metal salt and the spectroscopy measurement is preferably performed at a organic solvent, d / c is preferably within a range of 0.36sd / condition where the effect of moisture in the atmosphere can cs0.54 and more preferably within a range of 0.39sd / be lessened or ignored . For example, performing the IR cs0.48 . 65 measurement under a low humidity or zero humidity con Since the electrolytic solution of the present invention has dition such as in a dry room or a glovebox is preferable, or the metal salt and the organic solvent exist in a different performing the Raman measurement in a state where the US 11,011,781 B2 19 20 electrolytic solution of the present invention is kept inside a TABLE 2 - continued sealed container is preferable . Here , specific description is provided regarding a peak of Wave the electrolytic solution of the present invention containing Organic solvent number ( cm ) Attribution LiTFSA as the metal salt and acetonitrile as the organic 5 Acetic anhydride 1785 , 1826 Double bond between C and O solvent. Acetone 1727 Double bond between C and O Acetonitrile 2285 Triple bond between C and N When the IR measurement is performed on acetonitrile Acetonitrile 899 C single bond alone , a peak derived from stretching vibration of a triple DME 1099 O single bond bond between C and N is ordinarily observed at around 2100 DME 1124 C - o single bond 10 N ,N 1708 Double bond between C and O to 2400 cm - 1 . Dimethylformamide Here , based on conventional technical common knowl Y - Butyrolactone 1800 Double bond between C and O edge , a case is envisioned in which an electrolytic solution Nitropropane 1563 Double bond between N and O is obtained by dissolving LiTFSA in an acetonitrile solvent Pyridine 977 Unknown at a concentration of 1 mol/ L . Since 1 L of acetonitrile Dimethyl 1017 S – O bond corresponds to approximately 19 mol , 1 mol of LiTFSA and 15 sulfoxide 19 mol of acetonitrile exist in 1 L of a conventional electrolytic solution . Then , in the conventional electrolytic Regarding a wave number of an organic solvent and an solution , at the same time when acetonitrile solvated with attribution thereof, well- known data may be referenced . LiTFSA ( coordinated with Li ) exists, a large amount of Examples of the reference include “ Raman spectrometry ” acetonitrile not solvated with LiTFSA ( not coordinated with 20 Spectroscopical Society of Japan measurement method Li ) exists . Since an acetonitrile molecule solvated with series 17 , Hiroo Hamaguchi and Akiko Hirakawa, Japan LiTFSA and an acetonitrile molecule not solvated with Scientific Societies Press , pages 231 to 249. In addition , a LiTFSA are different regarding the environments in which wave number of an organic solvent considered to be useful the respective acetonitrile molecules are placed , the acetoni trile peaks of both molecules are distinctively observed in 25 for calculating Io and Is , and a shift in the wave number the IR spectrum . More specifically, although a peak of when the organic solvent and the metal salt coordinate with acetonitrile not solvated with LiTFSA is observed at the each other are predicted from a calculation using a computer. same position ( wavenumber ) as in the case with the IR For example, the calculation may be performed by using measurement on acetonitrile alone, a peak of acetonitrile Gaussian09 (Registered trademark , Gaussian , Inc. ), and solvated with LiTFSA is observed such that its peak position 30 setting the density function to B3LYP and the basis function ( wave number ) is shifted toward the high wave number side . to 6-3116 ++ ( d , p ) . A person skilled in the art can calculate Since a large amount of acetonitrile not solvated with lo and is by referring to the description in Table 2 , well LiTFSA exists at the concentration of the conventional known data , and a calculation result from a uter to electrolytic solution , the relationship between the intensity select a peak of an organic solvent. Io of the original peak of acetonitrile and the intensity Is of 35 Since the electrolytic solution of the present invention has the peak resulting from shift of the original peak of acetoni- the metal salt and the organic solvent exist in a different trile becomes Is < Io in the vibrational spectroscopy spectrum environment and has a high metal salt concentration when of the conventional electrolytic solution . compared to the conventional electrolytic solution ; improve On the other hand, when compared to the conventional ment in a metal ion transportation rate in the electrolytic electrolytic solution , the electrolytic solution of the present 40 solution ( particularly improvement of lithium transference invention has a high concentration of LiTFSA , and the number when the metal is lithium ), improvement in reaction number of acetonitrile molecules solvated ( forming a clus- rate between an electrode and an electrolytic solution inter ter ) with LiTFSA in the electrolytic solution is larger than face, mitigation of uneven distribution of salt concentration the number of acetonitrile molecules not solvated with in the electrolytic solution caused when a battery undergoes LiTFSA . As a result , the relationship between the intensity 45 high -rate charging and discharging , and increase in the Io of the original peak of acetonitrile and the intensity Is of capacity of an electrical double layer are expected . In the the peak resulting from shifting of the original peak of electrolytic solution of the present invention , since most of acetonitrile becomes Is > lo in the vibrational spectroscopy the organic solvent having the heteroelement is forming a spectrum of the electrolytic solution of the present inven cluster with the metal salt , the vapor pressure of the organic tion. 50 solvent contained in the electrolytic solution becomes lower . In Table 2 , wave numbers and attributions thereof are As a result , volatilization of the organic solvent from the exemplified for organic solvents considered to be useful electrolytic solution of the present invention is reduced . when calculating Io and is in the vibrational spectroscopy When compared to the electrolytic solution of a conven spectrum of the electrolytic solution of the present inven tional battery , the electrolytic solution of the present inven tion . Depending on measuring devices, measuring environ- 55 tion has a high viscosity. For example , a preferable Li ments, and measuring conditions used for obtaining the concentration of the electrolytic solution of the present vibrational spectroscopy spectrum , the wave number of the invention is about 2 to 5 times of the Li concentration of a observed peak may be different from the following wave general electrolytic solution . Thus , with a battery using the numbers . electrolytic solution of the present invention , even if the 60 battery is damaged , leakage of the electrolytic solution is suppressed . Furthermore , a secondary battery using the TABLE 2 conventional electrolytic solution has displayed a significant Wave reduction in capacity when subjected to high - speed charg Organic solvent number (cml ) Attribution ing /discharging cycles . The reason is conceivably the inabil Ethylene carbonate 1769 Double bond between C and O 65 ity of the electrolytic solution to supply sufficient amount of Propylene carbonate 1829 Double bond between C and O Li to a reaction interface with an electrode because of Li concentration unevenness generated in the electrolytic solu US 11,011,781 B2 21 22 tion when charging and discharging are repeated rapidly , i.e. , includes a liquid in which the metal salt is dissolved in the uneven distribution of Li concentration in the electrolytic organic solvent in a manner exceeding a conventionally solution . However, in a secondary battery using the electro- regarded saturation solubility . A method for producing the lytic solution of the present invention , the capacity was electrolytic solution of the present invention includes : a first shown to be suitably maintained during high - rate charging 5 dissolution step of preparing a first electrolytic solution by and discharging. A conceivable reason for that is the ability mixing the organic solvent having the heteroelement and the to suppress uneven distribution of the Li concentration in the metal salt to dissolve the metal salt ; a second dissolution step electrolytic solution due to a physical property regarding of preparing a second electrolytic solution in a supersatura having a high viscosity in the electrolytic solution of the tion state by adding the metal salt to the first electrolytic present invention . In addition , another conceivable reason is , 10 solution under stirring and / or heating conditions to dissolve due to the physical property regarding having a high vis- the metal salt ; and a third dissolution step of preparing a cosity in the electrolytic solution of the present invention , third electrolytic solution by adding the metal salt to the improvement in liquid retaining property of the electrolytic second electrolytic solution under stirring and / or heating solution at an electrode interface, resulting in suppression of conditions to dissolve the metal salt . a state of lacking the electrolytic solution at the electrode 15 Here, the “ supersaturation state ” described above refers to interface ( i.e. , liquid run - out state ). a state in which a metal salt crystal is deposited from the The electrolytic solution of the present invention contains electrolytic solution when the stirring and / or heating con a cation of the metal salt at a high concentration . Thus, the ditions are discontinued or when crystal nucleation energy distance between adjacent cations is extremely small within such as vibration is provided thereto . The second electrolytic the electrolytic solution of the present invention . When a 20 solution is in the " supersaturation state ,” whereas the first cation such as a lithium ion moves between a positive electrolytic solution and the third electrolytic solution are electrode and a negative electrode during charging and not in the “ supersaturation state .” discharging of the nonaqueous electrolyte secondary battery , In other words , with the method for producing the elec a cation located most closely to an electrode that is a trolytic solution of the present invention , via the first elec movement destination is firstly supplied to the electrode . 25 trolytic solution encompassing a conventional metal salt Then , to the place where the supplied cation had been concentration and being in a thermodynamically stable located, another cation adjacent to the cation moves . Thus , liquid state, and via the second electrolytic solution in a in the electrolytic solution of the present invention , a domino thermodynamically unstable liquid state , the third electro toppling - like phenomenon is predicted to be occurring in lytic solution , i.e. , the electrolytic solution of the present which adjacent cations sequentially change their positions 30 invention, in a thermodynamically stable new liquid state is one by one toward an electrode that is a supply target. obtained . Because of that, the distance for which a cation moves Since the third electrolytic solution in the stable liquid during charging and discharging is thought to be short, and state maintains its liquid state at an ordinary condition , in the movement speed of the cation is thought to be high , accord- third electrolytic solution , for example, a cluster, formed of ingly . Because of this reason , the nonaqueous electrolyte 35 2 molecules of the organic solvent with respect to 1 mol secondary battery of the present invention having the elec- ecule of a lithium salt and stabilized by a strong coordinate trolytic solution of the present invention is thought to have bond between these molecules , is estimated to be inhibiting a high reaction rate . As described later, the nonaqueous crystallization of the lithium salt . electrolyte secondary battery of the present invention The first dissolution step is a step of preparing the first includes an S , O - containing coating on the electrode ( i.e. , the 40 electrolytic solution by mixing the organic solvent having a negative electrode and / or the positive electrode ), and the heteroatom with the metal salt to dissolve the metal salt . S , O - containing coating is thought to largely include a cation For the purpose of mixing the organic solvent having a in addition to including the S = O structure . The cation heteroatom with the metal salt , the metal salt may be added included in the S , O - containing coating is thought to be with respect to the organic solvent having a heteroatom , or preferentially supplied to the electrode . Thus, in the non- 45 the organic solvent having a heteroatom may be added with aqueous electrolyte secondary battery of the present inven- respect to the metal salt . tion , transportation rate of the cation is thought to be further The first dissolution step is preferably performed under improved because of having an abundant source of cation stirring and / or heating conditions . The stirring speed may be ( i.e. , the S , O - containing coating ) in the vicinity of the set suitably. The heating condition is preferably controlled electrode. As a result, in the nonaqueous electrolyte second- 50 suitably using a temperature controlled bath such as a water ary battery of the present invention, excellent battery char- bath or an oil bath . Since dissolution heat is generated when acteristics are thought to be exerted because of a cooperation dissolving the metal salt, the temperature condition is pref between the electrolytic solution of the present invention erably strictly controlled when a metal salt that is unstable and the S , O -containing coating . against heat is to be used . In addition , the organic solvent The method for producing the electrolytic solution of the 55 may be cooled in advance , or the first dissolution step may present invention is described . Since the electrolytic solution be performed under a cooling condition . of the present invention contains a large amount of the metal The first dissolution step and the second dissolution step salt compared to the conventional electrolytic solution , a may be performed continuously , or the first electrolytic production method of adding the organic solvent to a solid solution obtained from the first dissolution step may be ( powder ) metal salt results in an aggregate , and manufac- 60 temporarily kept ( left still ) , and the second dissolution step turing an electrolytic solution in a solution state is difficult. may be performed after a certain period of time has elapsed . Thus, in the method for producing the electrolytic solution The second dissolution step is a step of preparing the of the present invention , the metal salt is preferably gradu- second electrolytic solution in the supersaturation state by ally added to the organic solvent while a solution state of the adding the metal salt to the first electrolytic solution under electrolytic solution is maintained during production . 65 stirring and / or heating conditions to dissolve the metal salt . Depending on the types of the metal salt and the organic Performing the second dissolution step under the stirring solvent, the electrolytic solution of the present invention and /or heating conditions is essential for preparing the US 11,011,781 B2 23 24 second electrolytic solution in the thermodynamically copy measurement may be performed , or a method in which unstable supersaturation state . The stirring condition may be vibrational spectroscopy measurement is conducted on each obtained by performing the second dissolution step in a of the electrolytic solutions in situ may be performed . stirring device accompanied with a stirrer such as a mixer, Examples of the method of conducting the vibrational or the stirring condition may be obtained by performing the 5 spectroscopy measurement on the electrolytic solution in second dissolution step using a stirring bar and a device situ include a method of introducing the electrolytic solution ( stirrer ) for moving the stirring bar. The heating condition is that is being produced in a transparent flow cell and con preferably controlled suitably using a temperature controlled ducting the vibrational spectroscopy measurement, and a bath such as a water bath or an oil bath . Needless to say , method of using a transparent production container and performing the second dissolution step using an apparatus or 10 conducting Raman measurement from outside the container . a system having both a stirring function and a heating Since the relationship between Is and Io in an electrolytic function is particularly preferable. "Heating " described here solution that is being produced is confirmed by including the refers to warming an object to a temperature not lower than vibrational spectroscopy measurement step in the method an ordinary temperature ( 25 ° C. ) . The heating temperature is for producing the electrolytic solution of the present inven more preferably not lower than 30 ° C. and further preferably 15 tion , whether or not an electrolytic solution that is being not lower than 35 ° C. In addition, the heating temperature is produced has reached the electrolytic solution of the present preferably a temperature lower than the boiling point of the invention is determined , and, when an electrolytic solution organic solvent. that is being produced has not reached the electrolytic In the second dissolution step , when the added metal salt solution of the present invention , how much more of the does not dissolve sufficiently , increasing the stirring speed 20 metal salt is to be added for reaching the electrolytic solution and / or further heating are performed . In this case , a small of the present invention is understood . amount of the organic solvent having a heteroatom may be To the electrolytic solution of the present invention , other added to the electrolytic solution in the second dissolution than the organic solvent having the heteroelement, a solvent step . that has a low polarity ( low permittivity ) or a low donor Since temporarily leaving still the second electrolytic 25 number and that does not display particular interaction with solution obtained in the second dissolution step causes the metal salt , i.e. , a solvent that does not affect formation deposition of crystal of the metal salt , the second dissolution and maintenance of the cluster in the electrolytic solution of step and the third dissolution step are preferably performed the present invention , may be added . Adding such a solvent continuously. to the electrolytic solution of the present invention is The third dissolution step is a step of preparing the third 30 expected to provide an effect of lowering the viscosity of the electrolytic solution by adding the metal salt to the second electrolytic solution of the present invention while main electrolytic solution under stirring and / or heating conditions taining the formation of the cluster in the electrolytic solu to dissolve the metal salt . In the third dissolution step , since tion of the present invention . adding and dissolving the metal salt in the second electro- Specific examples of the solvent that does not display lytic solution in the supersaturation state are necessary, 35 particular interaction with the metal salt include benzene, performing the step under stirring and /or heating conditions toluene, ethylbenzene, O -xylene , m - xylene, p - xylene, similarly to the second dissolution step is essential . Specific 1 -methylnaphthalene , hexane , heptane, and cyclohexane. stirring and / or heating conditions are similar to the condi- In addition , to the electrolytic solution of the present tions for the second dissolution step . invention , a fire - resistant solvent other than the organic When the mole ratio of the organic solvent and the metal 40 solvent having the heteroelement may be added . By adding salt added throughout the first dissolution step , the second the fire - resistant solvent to the electrolytic solution of the dissolution step , and the third dissolution step reaches present invention , safety of the electrolytic solution of the roughly about 2 : 1 , production of the third electrolytic solu- present invention is further enhanced. Examples of the tion ( the electrolytic solution of the present invention ) ends . fire -resistant solvent include halogen based solvents such as A metal salt crystal is not deposited from the electrolytic 45 carbon tetrachloride , tetrachloroethane, and hydrofluo solution of the present invention even when the stirring roether, and phosphoric acid derivatives such as trimethyl and / or heating conditions are discontinued . Based on these phosphate and triethyl phosphate . circumstances, in the electrolytic solution of the present Furthermore, when the electrolytic solution of the present invention , for example , a cluster, formed of 2 molecules of invention is mixed with a polymer or an inorganic filler to the organic solvent with respect to 1 molecule of a lithium 50 form a mixture, the mixture enables containment of the salt and stabilized by a strong coordinate bond between electrolytic solution to provide a pseudo solid electrolyte . these molecules , is estimated to be formed . By using the pseudo solid electrolyte as an electrolytic When producing the electrolytic solution of the present solution of a battery, leakage of the electrolytic solution is invention , even without via the supersaturation state at suppressed in the battery . processing temperatures of each of the dissolution steps , the 55 As the polymer, a polymer used in batteries such as electrolytic solution of the present invention is suitably lithium ion secondary batteries and a general chemically produced using the specific dissolution means described in cross - linked polymer are used . In particular, a polymer the first to third dissolution steps depending on the types of capable of turning into a gel by absorbing an electrolytic the metal salt and the organic solvent. solution , such as polyvinylidene fluoride and polyhexafluo In addition , the method for producing the electrolytic 60 ropropylene, and one obtained by introducing an ion con solution of the present invention preferably includes a ductive group to a polymer such as polyethylene oxide are vibrational spectroscopy measurement step of performing suitable . vibrational spectroscopy measurement on the electrolytic Specific examples of the polymer include polymethyl solution that is being produced . As a specific vibrational acrylate, polymethacrylate, polymethyl methacrylate , poly spectroscopy measurement step , for example, a method in 65 ethylene oxide , polypropylene oxide , polyacrylonitrile, which a portion of each of the electrolytic solutions being polyvinylidene fluoride, polyethylene glycol dimethacry produced is sampled to be subjected to vibrational spectros- late , polyethylene glycol acrylate , polyglycidol, polytet US 11,011,781 B2 25 26 rafluoroethylene, polyhexafluoropropylene , polysiloxane, The nonaqueous electrolyte secondary battery includes a polyvinyl acetate , polyvinyl alcohol, polyacrylic acid , negative electrode having a negative electrode active mate polymethacrylic acid , polyitaconic acid , polyfumaric acid , rial configured to occlude and release a charge carrier such polycrotonic acid , polyangelic acid , polycarboxylic acid as lithium ions , a positive electrode having a positive such as carboxymethyl cellulose , styrene -butadiene rubbers, 5 electrode active material configured to occlude and release nitrile - butadiene rubbers , polystyrene, polycarbonate, the charge carrier, and the electrolytic solution of the present unsaturated polyester obtained through copolymerization of invention . The electrolytic solution of the present invention maleic anhydride and glycols , polyethylene oxide deriva is particularly suitable as an electrolytic solution for lithium tives having a substituent group , and a copolymer of ion secondary batteries since a lithium salt is used as the vinylidene fluoride and hexafluoropropylene . In addition , as 10 the polymer, a copolymer obtained through copolymeriza metal salt . tion of two or more types of monomers forming the above < Negative Electrode > described specific polymers may be selected . The negative electrode includes a current collector and a Polysaccharides are also suitable as the polymer. Specific negative electrode active material layer bound to the surface examples of the polysaccharides include glycogen , cellu- 15 of the current collector. lose , chitin , agarose , carrageenan , heparin, hyaluronic acid , [ Current Collector ] pectin , amylopectin, xyloglucan , and amylose. In addition , The current collector refers to a fine electron conductor materials containing these polysaccharides may be used as that is chemically inert for continuously sending a flow of the polymer, and examples of the materials include agar current to the electrode during discharging or charging of the containing polysaccharides such as agarose . 20 nonaqueous electrolyte secondary battery. Examples of the As the inorganic filler, inorganic ceramics such as oxides current collector include at least one selected from silver, and nitrides are preferable. copper, gold , aluminum , tungsten , cobalt , zinc , nickel , iron , Inorganic ceramics have hydrophilic and hydrophobic platinum , tin , indium , titanium , ruthenium , tantalum , chro functional groups on their surfaces . Thus, a conductive mium , or molybdenum , and metal materials such as stainless passage may form within the inorganic ceramics when the 25 steel . The current collector may be coated with a protective functional groups attract the electrolytic solution . Further layer known in the art . One obtained by treating the surface more , the inorganic ceramics dispersed in the electrolytic of the current collector with a method known in the art may solution form a network among the inorganic ceramics themselves due to the functional groups , and may serve as be used as the current collector . containment of the electrolytic solution . With such a func- 30 The current collector takes forms such as a foil, a sheet, tion by the inorganic ceramics, leakage of the electrolytic a film , a line shape, a bar shape, and a mesh . Thus, as the solution in the battery is further suitably suppressed . In order current collector, for example, metal foils such as copper to have the inorganic ceramics suitably exert the function foil, nickel foil, and stainless steel foil may be suitably used . described above, the inorganic ceramics having a particle When the current collector is in the form of a foil, a sheet, shape are preferable, and those whose particle sizes are nano 35 or a film , its thickness is preferably within a range of 1 um level are particularly preferable. to 100 um . Examples of the types of the inorganic ceramics include [ Negative Electrode Active Material Layer] common alumina , silica , titania , zirconia , and lithium phos The negative electrode active material layer includes a phate. In addition , inorganic ceramics that have lithium negative electrode active material and a general binder. The conductivity themselves are preferable, and specific 40 negative electrode active material layer may further include examples thereof include LizN , Lil , Lil - LizN - LiOH , a conductive additive if necessary . Lil — Li , S_P , 05, Lil - Li SP, , S5, Lil - Li , SB , S3 , < Nonaqueous Electrolyte Secondary Battery ( 1 ) > Li20B2S3 , Li20 — V203Si02 , Li20B203 - P205, The negative electrode active material in the nonaqueous Li , OB , 02 Zno , Li , O - A1,0 , –TiO2SiO , P , 05, electrolyte secondary battery ( 1 ) includes a graphite whose LiTi, (PO4 ) 3, Li - BA1,03 , and LiTaOz. 45 G / D ratio is not lower than 3.5 . The G / D ratio is a ratio of Glass ceramics may be used as the inorganic filler . Since G - band and D - band peaks in a Raman spectrum as described glass ceramics enables containment of ionic liquids, the above . In a Raman spectrum for graphite, peaks appear at same effect is expected for the electrolytic solution of the G - band ( around 1590 cm- ? ) and D - band ( around 1350 present invention . Examples of the glass ceramics include cm- ' ) , and G - band is derived from a graphite structure and compounds represented by xLi2S- ( 1 - x ) P2S5 , and those in 50 D - band is derived from defects . Thus, having a higher G / D which one portion of S in the compound is substituted with ratio , which is the ratio of G - band and D -band , means the another element and those in which one portion of P in the graphite has high crystallinity with less defects. Hereinafter, compound is substituted with germanium . a graphite whose G / D ratio is not lower than 3.5 is some Since the electrolytic solution of the present invention times referred to as a high -crystallinity graphite , and a described above displays excellent ionic conductivity, the 55 graphite whose G / D ratio is lower than 3.5 is sometimes electrolytic solution is suitably used as an electrolytic solu- referred to as a low - crystallinity graphite . tion of a power storage device such as a battery. In particular, As such a high - crystallinity graphite , both natural graphi the electrolytic solution is preferably used as electrolytic tes and artificial graphites may be used . When a classifica solutions of secondary batteries, and , among those , prefer- tion method based on shape is used , flake - like graphites, ably used as electrolytic solutions of lithium ion secondary 60 spheroidal graphites, block - like graphites, and earthy batteries . graphites may also be used . In addition , coated graphites In the following, description of the nonaqueous electro- obtained by coating the surface of a graphite with a carbon lyte secondary battery of the present invention using the material or the like may also be used . electrolytic solution of the present invention is provided . As long as the high - crystallinity graphite whose G / D ratio Unless mentioned otherwise in particular in the following, 65 is not lower than 3.5 is included as a main component, the the description is regarding all the nonaqueous electrolyte negative electrode active material may include the low secondary batteries ( 1 ) to ( 5 ) of the present invention . crystallinity graphite or amorphous carbon . US 11,011,781 B2 27 28 < Nonaqueous Electrolyte Secondary Battery ( 2 ) > expands and contracts ) associated with occlusion and release The negative electrode active material in the nonaqueous lithium ions . The silicon oxide phase is formed of SiO , etc., electrolyte secondary battery ( 2 ) includes a carbon material and changes less in volume associated with charging and whose crystallite size is not larger than 20 nm . As described discharging when compared to the Si phase. Thus, SiO used above , the crystallite size is calculated from a half width of 5 as the negative electrode active material achieves higher a peak appearing at 20 = 20 degrees to 30 degrees in a X - ray capacity because of the Si phase , and , when included in the diffraction profile measured by X - ray diffraction method . A silicon oxide phase , suppresses change of the whole volume larger crystallite size means atoms are arranged periodically of the negative electrode active material ( or the negative and precisely in accordance with a certain rule . On the other electrode ). When “ X ” becomes smaller than a lower limit hand , a carbon material whose crystallite size is not larger 10 value , cycle characteristics deteriorate since the change in than 20 nm is considered to be in a poorly periodical and volume during charging and discharging becomes too large precise state . For example, when the carbon material is a due to the ratio of Si becoming excessive . On the other hand, graphite, the crystallite size becomes not larger than 20 nm when “ x ” becomes larger than an upper limit value , energy when the size of a graphite crystal is not larger than 20 nm density is decreased due to the Si ratio being too small . The or when atoms forming the graphite are arranged irregularly 15 range of “ x ” is more preferably 0.5sxs1.5 and further due to distortion , defects, and impurities , etc. Using a carbon preferably 0.7sxs1.2 . material whose crystallite size is not larger than 5 nm in the In SiO , described above, an alloying reaction between nonaqueous electrolyte secondary battery ( 2 ) of the present lithium element and silicon element included in the Si phase invention is particularly preferable. is thought to occur during charging and discharging of the Although representative examples of the carbon material 20 nonaqueous electrolyte secondary battery. This alloying whose crystallite size is not larger than 20 nm are hard reaction is thought to contribute to charging and discharging carbon and soft carbon , “ the carbon material whose crys- of the nonaqueous electrolyte secondary battery ( lithium ion tallite size is not larger than 20 nm ” in the nonaqueous secondary battery in this case ) . Also in the negative elec electrolyte secondary battery ( 2 ) of the present invention is trode active material including tin element described later, not limited thereto . 25 charging and discharging are thought to occur by an alloying In order to measure the crystallite size of the carbon reaction between tin element and lithium element similarly. material, an X -ray diffraction method using Cu K - a radia- Examples of the negative electrode active material includ tion as an X -ray source may be used . From the X - ray ing tin element include Sn elemental substance, tin alloys diffraction method, the crystallite size is calculated using the ( Cu — Sn alloys , Co — Sn alloys ) , amorphous tin oxides , and next Scherrer's equation based on a half width of a diffrac- 30 tin silicon oxides , etc. Among these, examples of the amor tion peak detected at a diffraction angle of 20 = 20 degrees to phous tin oxides include SnBo.410.03.1. Examples of the tin 30 degrees and the diffraction angle . silicon oxides include SnSiOz . The above described negative electrode active material L = 0.941 ( ß cos 0 ) including silicon element and the negative electrode active wherein 35 material including tin element may also be used as a L : Crystallite size composite with a material containing carbon element ( car a : Incident X - ray wavelength ( 1.54 Å ) bon material ). By using these as a composite instead of B : Half width of peak ( radian ) independently , the structure of particularly silicon and / or tin 0 : Diffraction angle stabilizes , and durability of the negative electrode improves. < Nonaqueous Electrolyte Secondary Battery ( 3 ) > 40 Specifically , the carbon material such as graphite is a mate The negative electrode active material in the nonaqueous rial showing less volume change during charging and dis electrolyte secondary battery ( 3 ) includes silicon element charging, when compared to elemental substance silicon and and / or tin element. Silicon and tin are known negative elemental substance tin . Thus , by forming a composite of electrode active materials capable of greatly improving the such a carbon material with the negative electrode active capacity of a nonaqueous electrolyte secondary battery. 45 material including silicon element and the negative electrode Silicon and tin belong to group 14 elements . These elemen- active material including tin element, damage or the like to tal substances become negative electrode active materials the negative electrode caused by volume change during with high capacity since being configured to occlude and charging and discharging is suppressed , and durability of the release a large amount of charge carriers ( lithium ions , etc. ) negative electrode improves. As a result , cycle characteris per unit volume ( mass ) . However, a nonaqueous electrolyte 50 tics of the nonaqueous electrolyte secondary battery secondary battery using those as the negative electrode improve . A known method may be used for forming a active material has relatively poor rate characteristics. composite of the carbon material with the negative electrode On the other hand, a nonaqueous electrolyte secondary active material including silicon element and / or the negative battery using carbon as the negative electrode active mate- electrode active material including tin element . rial has excellent rate characteristics. Thus, by using both as 55 As the carbon material that is to be formed into a the negative electrode active material, the nonaqueous elec- composite with the negative electrode active material trolyte secondary battery obtains a high capacity, and excel- including silicon element and / or the negative electrode lent rate characteristics are provided to the nonaqueous active material including tin element, graphite, hard carbon electrolyte secondary battery . ( hardly graphitizable carbon ), soft carbon ( easily graphitiz Although the theoretical capacity is large when silicon is 60 able carbon ), and the like are used preferably. Regarding the used as the negative electrode active material, the change in graphite, natural and artificial graphites may be used , and its volume during charging and discharging is large . Thus, as particle size is not particularly limited . the negative electrode active material including silicon ele- < Nonaqueous Electrolyte Secondary Battery ( 4 ) ment, using SiO , ( 0.3sxsl.6 ) disproportionated into two The negative electrode active material in the nonaqueous phases of Si phase and silicon oxide phase is particularly 65 electrolyte secondary battery ( 4 ) includes a metal oxide preferable. The Si phase in Sio is configured to occlude and configured to occlude and release lithium ions . Examples of release lithium ions . The Si phase changes in volume ( i.e. , the metal oxide include titanium oxides such as TiO2 , US 11,011,781 B2 29 30 lithium titanium oxides , tungsten oxides such as WO3 , due to its crystal structure . When a graphite having a flat amorphous tin oxides, and tin silicon oxides . shape is arranged in the negative electrode active material Specific examples of the lithium titanium oxides include layer, the proportion of basal surfaces of graphite crystals lithium titanate having a spinel structure ( e.g. , Li4 + xTis + 2012 orientated parallelly to the surface of the current collector ( x and y respectively satisfy -1sxs4 and -1sysl )) and 5 increases, and diffraction intensity such as I ( 002 ) derived lithium titanate having a ramsdellite structure ( e.g. , from the basal surface becomes relatively strong in an XRD Li Tiz07) . Specific examples of the amorphous tin oxides analysis . include SnB . 4P0.603.1. Specific examples of the tin silicon By using this feature and investigating a ratio [ I ( 110 ) / I oxides include SnSiO3 . Usage of lithium titanate having a ( 004 ) ] with a diffraction intensity derived from a crystal spinel structure is particularly preferable, which is further 10 surface different from the basal surface such as I ( 110 ) , specifically Li Ti- 012 . In such a lithium ion secondary information regarding how much of flat shaped graphite is battery that includes lithium titanate as the negative elec- included is indirectly investigated . Thus, the graphite used in trode, reactions for occluding and releasing lithium are the present invention preferably has I ( 110 ) / I ( 004 ) in a range thought to occur stably, and , as a result , degradation of an of 0.03 to 1. By using such a graphite, input- output char active material is thought to be suppressed . Thus, a lithium 15 acteristics improve since arrangement of flat particles ion secondary battery having this type of metallic compound becomes less and the diffusion pathway of the electrolytic as a negative electrode active material is known to have solution in the negative electrode active material layer superior cycle characteristics . By using the metal oxide with becomes short. the nonaqueous electrolyte secondary battery of the present The graphite particles preferably have a BET specific invention using the electrolytic solution of the present 20 surface area within a range of 0.5 to 15 m3 / g . When the BET invention , a nonaqueous electrolyte secondary battery specific surface area becomes larger than 15 mº / g , side capable of achieving both the excellent battery characteris- reaction with the electrolytic solution tends to accelerate . tics derived from the electrolytic solution of the present When the BET specific surface area becomes smaller than invention and excellent cycle characteristics is obtained . 0.5 mº / g , input /output sometimes deteriorate since the reac < Nonaqueous Electrolyte Secondary Battery ( 5 ) > 25 tion resistance becomes large. The negative electrode active material in nonaqueous As long as the graphite whose aspect ratio is 1 to 5 is used electrolyte secondary battery ( 5 ) includes a graphite whose as a main component, the negative electrode active material ratio ( long axis / short axis ) of long axis to short axis is 1 to may include a graphite , amorphous carbon , or the like whose 5. Representative graphites whose ratio ( long axis / short aspect ratio is outside this range . axis ) of long axis to short axis is 1 to 5 include spheroidal 30 The nonaqueous electrolyte secondary batteries ( 1 ) to ( 5 ) graphites, MCMB (meso carbon micro beads ) , and the like. of the present invention may include, in addition to the Spheroidal graphites are carbon materials such as artificial characteristic negative electrode active material that is used graphites, natural graphites , easily graphitizable carbon , and in each of the nonaqueous electrolyte secondary batteries , hardly graphitizable carbon , and refer to those whose shapes another negative electrode active material configured to are spheroidal or almost spheroidal. 35 occlude and release a charge carrier. Hereinafter, if neces Spherical graphite particles are obtained by grinding sary, the other negative electrode active material is referred material graphite in an impact grinder having a relatively to as a secondary negative electrode active material. In small crushing force , and collecting and then spheroidizing addition , the characteristic negative electrode active material the resulting flakes through compression . As the impact in each of the nonaqueous electrolyte secondary batteries of grinder, for example, a hammer mill or a pin mill is used . An 40 the present invention is referred to as a primary negative outer - circumference line speed of a rotating hammer or pin electrode active material. For example , when the nonaque is preferable about 50 to 200 m / s . Supply and ejection of ous electrolyte secondary battery of the present invention is graphite with respect to such grinders are preferably per- a lithium ion secondary battery , the secondary negative formed in association with a current of air or the like . electrode active material is not particularly limited as long as The degree of spheroidization of graphite particles is 45 the secondary negative electrode active material is an represented by the ratio of long axis to short axis ” ( long elemental substance, an alloy, or a compound configured to axis / short axis , hereinafter referred to as “ aspect ratio ” ) . occlude and release a charge carrier, i.e. , lithium ion . Thus, in an arbitrary cross section of a graphite particle, Examples of the elemental substance used as the secondary when , among axis lines that perpendicularly intersect at the negative electrode active material include respective center of gravity, those who have the largest aspect ratio are 50 elemental substances of Li , group 14 elements such as selected ; an aspect ratio close to 1 means close to being a carbon , silicon , germanium and tin , group 13 elements such true sphere. With the above described spheroidization pro- as aluminum and indium , group 12 elements such as zinc cess , the aspect ratio is easily set equal to or lower than 5 ( 1 and cadmium , group 15 elements such as antimony and to 5 ) . When the spheroidization process is performed suffi- bismuth , alkaline earth metals such as magnesium and ciently, the aspect ratio is set equal to or lower than 3 ( 1 to 55 calcium , and group 11 elements such as silver and gold . 3 ) . The graphite used in the present invention has a particle When silicon or the like is used as the secondary negative aspect ratio of 1 to 5 , and preferably 1 to 3. When the aspect electrode active material, a high capacity active material is ratio is set equal to or lower than 5 , a diffusion pathway of obtained since a single silicon atom reacts with multiple the electrolytic solution in the negative electrode active lithium ions . However, a fear of occurrence of a problem material layer becomes short. As a result , since resistance 60 regarding a significant expansion and contraction of volume component caused by the electrolytic solution is reduced , associated with occlusion and release of lithium exists . In improvement of input and output is thought to be possible . order to mitigate the fear, an alloy or a compound obtained When the aspect ratio is set to 1 , the graphite becomes a by combining an elemental substance such as silicon with shape closest to a true sphere , and the diffusion pathway of another element such as a transition metal is suitably used as the electrolytic solution is set to be the shortest. 65 the secondary negative electrode active material. Specific Graphite is capable of easily taking a flat shape since examples of the alloy or the compound include tin based having a property of being easily cracked at a basal surface materials such as Ag - Sn alloys , Cu - Sn alloys , and Co US 11,011,781 B2 31 32 Sn alloys , carbon based materials such as various graphites , ing conductivity of the electrode. Thus, the conductive silicon based materials such as SiO , ( 0.3sxs1.6 ) that under- additive is preferably added optionally when conductivity of goes disproportionation into the elemental substance silicon an electrode is insufficient, and does not have to be added and silicon dioxide , and a complex obtained by combining when conductivity of an electrode is sufficiently superior. As a carbon based material with elemental substance silicon or 5 the conductive additive , a fine electron conductor that is a silicon based material. In addition , as the secondary chemically inert may be used , and examples thereof include negative electrode active material, an oxide such as Nb205, carbonaceous fine particles such as carbon black , graphite , TiO2 , Li Ti 0.2, WO2 , Mo02 , and FE2O3, or a nitride acetylene black , Ketchen black ( Registered Trademark ), and represented by Liz M N ( M = Co , Ni , Cu ) may be used . vapor grown carbon fiber ( VGCF ) . With regard to the With regard to the secondary negative electrode active 10 conductive additive described above, a single type by itself, material, one or more types described above may be used . or a combination of two or more types may be added to the By using the primary negative electrode active material active material layer. The blending ratio of the conductive with the various secondary negative electrode active mate- additive in the negative electrode active material layer is not rials described above , further excellent battery characteris- particularly limited , but is preferably, in mass ratio , negative tics are provided to the nonaqueous electrolyte secondary 15 electrode active material: conductive additive = 1 :0.01 to battery. For example , in the nonaqueous electrolyte second- 1 : 0.5 . The reason is that when too little of the amount of the ary battery ( 4 ) , by using any of the above described sec- conductive additive is contained , efficient conducting paths ondary negative electrode active materials with a metal cannot be formed , whereas when the amount of the conduc oxide as the primary negative electrode active material, the tive additive is too large, moldability of the negative elec nonaqueous electrolyte secondary battery obtains a higher 20 trode active material layer deteriorates and energy density of capacity compared to when the metal oxide is used by itself. the electrode becomes low . When the primary negative electrode active material and the The negative electrode of the nonaqueous electrolyte secondary negative electrode active material are used secondary battery is produced by : applying, on the current together, the main component of the negative electrode collector using a method such as roll coating method , dip active material is preferably the primary negative electrode 25 coating method , doctor blade method , spray coating method , active material. Specifically, with respect to the entire nega- and curtain coating method , a slurry obtained through add tive electrode active material, the primary negative electrode ing and mixing the negative electrode active material pow active material preferably accounts for not less than 50 mass der, the conductive additive such as a carbon powder, the % and more preferably not less than 80 mass % . This also binder, and a proper amount of a solvent; and drying mixture applies for the negative electrode active materials in other 30 or curing the binder . Examples of the solvent include nonaqueous electrolyte secondary batteries. N -methyl - 2 - pyrrolidone , methanol, methyl isobutyl ketone, In addition , in the nonaqueous electrolyte secondary and water . In order to increase electrode density, compres battery ( 4 ) , the above described metal oxide based negative sion may be performed after drying. electrode active material includes, as a main component, at < Positive Electrode > least one type selected from titanium oxides , lithium tita- 35 The positive electrode used in the nonaqueous electrolyte nium oxides , tungsten oxides , amorphous tin oxides , and tin secondary battery includes the positive electrode active silicon oxides . The " main component” described herein material configured to occlude and release a charge carrier. refers to a corresponding component that is included by not The positive electrode includes the current collector and the less than 50 mass % of a population that forms the basis . positive electrode active material layer bound to the surface Specifically, when the entirety of the metal oxide capable of 40 of the current collector. The positive electrode active mate functioning as the negative electrode active material is rial layer includes the positive electrode active material, and, defined as 100 mass % , the main component ( i.e. , at least if necessary , the binding agent and / or the conductive addi one type selected from titanium oxides , lithium titanium tive . The current collector of the positive electrode is not oxides , tungsten oxides , amorphous tin oxides , and tin particularly limited as long as the current collector is a metal silicon oxides ) is included by not less than 50 mass % . The 45 capable of withstanding a voltage suited for the active negative electrode may include other unavoidable contents , material that is used . Examples of the current collector and examples thereof include at least one element selected include at least one selected from silver, copper , gold , from Li , Fe , Cr, Cu , Zn , Ca , Mg , S , Si , Na , K , Al , Zr, Ti , P , aluminum , tungsten , cobalt , zinc, nickel, iron , platinum , tin , Ga , Ge , V , Mo , Nb , W , and La . indium , titanium , ruthenium , tantalum , chromium , or The binder serves a role of fastening the active material 50 molybdenum , and metal materials such as stainless steel . and the conductive additive to the surface of the current When the nonaqueous electrolyte secondary battery of the collector. present invention is a lithium ion secondary battery, and Examples of the binder include fluorine - containing resins when the potential of the positive electrode is set to not such as polyvinylidene fluoride, polytetrafluoroethylene, lower than 4 V using lithium as reference , a current collector and fluororubbers, thermoplastic resins such as polypropyl- 55 made from aluminum is preferably used . ene and polyethylene, imide based resins such as polyimide The electrolytic solution of the present invention is and polyamide - imide , alkoxysilyl group - containing resins, unlikely to corrode a current collector made from aluminum . and polymers having a hydrophilic group such as poly- Thus , the nonaqueous electrolyte secondary battery using acrylic acid ( PAA ) and carboxymethyl cellulose ( CMC ) . the electrolytic solution of the present invention and the The blending ratio of the binder in the negative electrode 60 aluminum current collector on the positive electrode is active material layer is preferably negative electrode active thought unlikely to cause elution of Al even at a high material :binder = 1 : 0.005 to 1 : 0.3 . When the amount of the potential. Although the reason why elution of Al is unlikely binder is too small , moldability of the electrode deteriorates, to occur is unclear, the electrolytic solution of the present whereas, when the amount of the binder is too large , energy invention is different from the conventional electrolytic density of the electrode becomes low . 65 solution regarding the types and existing environment of the The conductive additive included in the negative elec- metal salt and the organic solvent and the concentration of trode active material layer if necessary is added for increas- the metal salt . Thus, solubility of Al with respect to the US 11,011,781 B2 33 34 electrolytic solution of the present invention is speculated to nitroxide , galvinoxyl , and phenoxyl may be used as the be low when compared to a conventional electrolytic solu- positive electrode active material. tion . When a raw material for the positive electrode active Specifically , one formed from aluminum or an aluminum material not containing a charge carrier such as lithium is to alloy is preferably used as the positive electrode current 5 be used , a charge carrier has to be added in advance to the collector. Here , aluminum refers to pure aluminum , and an positive electrode and / or the negative electrode using a aluminum whose purity is equal to or higher than 99.0 % is method known in the art. Specifically, the charge carrier may referred to as pure aluminum . An alloy obtained by adding be added in an ionic state , or may be added in a nonionic various elements to pure aluminum is referred to as an state such as a metal or a compound. For example, a lithium aluminum alloy. Examples of the aluminum alloy include 10 foilpositive or the electrode like may and be / or pastedthe negative to , and electrode integrated . Similarly with the to those that are Al_Cu based , Al - Mn based , Al - Fe based , the negative electrode, the positive electrode may include a Al — Si based , Al - Mg based , AL - Mg - Si based , and conductive additive , a binder, and the like . The conductive Al - Zn - Mg based . additive and the binder are not particularly limited as long as In addition , specific examples of aluminum or the alumi 15 the conductive additive and the binder are usable in a num alloy include A1000 series alloys ( pure aluminum nonaqueous electrolyte secondary battery, similarly to the based ) such as JIS A1085 , A1N30 , etc., A3000 series alloys negative electrode. ( Al - Mn based ) such as JIS A3003 , A3004 , etc. , and A8000 In order to form the active material layer on the surface of series alloys ( A1 — Fe based ) such as JIS A8079 , A8021 , etc. the current collector, the active material may be applied on The current collector may be coated with a protective 20 the surface of the current collector using a conventional layer known in the art . One obtained by treating the surface method known in the art such as roll coating method , die of the current collector with a method known in the art may coating method , dip coating method, doctor blade method , be used as the current collector. spray coating method , and curtain coating method . Specifi The current collector takes forms such as a foil, a sheet, cally, an active material layer forming composition includ a film , a line shape, a bar shape, and a mesh . Thus, as the 25 ing the active material and , if necessary , the binding agent current collector, for example , metal foils such as copper and the conductive additive is prepared , and , after adding a foil, nickel foil, aluminum foil, and stainless steel foil are suitable solvent to this composition to obtain a paste , the suitably used . When the current collector is in the form of a paste is applied on the surface of the current collector and foil, a sheet , or a film , its thickness is preferably within a then dried . Examples of the solvent include N -methyl - 2 range of 1 um to 100 um . 30 pyrrolidone , methanol, methyl isobutyl ketone, and water . In The binding agent and the conductive additive of the order to increase electrode density , compression may be positive electrode are similar to those described in relation performed after drying. to the negative electrode. A separator is used in the nonaqueous electrolyte second Examples of the positive electrode active material include ary battery, if necessary. The separator is for separating the layer compounds that are Li, Ni, Co Mn, D 0 , ( 0.2sasl.2 ; 35 positive electrode and the negative electrode to allow pas b + c + d + e = 1 ; 0se < 1 ; D is at least one element selected from sage of lithium ions while preventing short circuiting of Li , Fe , Cr, Cu , Zn , Ca , Mg , S , Si , Na , K , A1 , Zr, Ti , P , Ga , current due to a contact of both electrodes. Examples of the Ge , V , Mo , Nb , W , or La ; 1.7sfs2.1 ) and LizMnOz. Addi- separator include porous materials, nonwoven fabrics, and tional examples of the positive electrode active material woven fabrics using one or more types of materials having include spinel such as LiMn204, a solid solution formed 40 electrical insulation property such as : synthetic resins such from a mixture of spinel and a layer compound, and poly- as polytetrafluoroethylene , polypropylene , polyethylene, anion based compounds such as LiMPO4 , LiMVO4, or polyimide , polyamide , polyaramide ( aromatic polyamide ), LizMSI04 (wherein , “ M ” is selected from at least one of Co , polyester, and polyacrylonitrile; polysaccharides such as Ni , Mn , or Fe ) . cellulose and amylose ; natural polymers such as fibroin , Further additional examples of the positive electrode 45 keratin , lignin , and suberin ; and ceramics . In addition , the active material include favorite based compounds repre- separator may have a multilayer structure . Since the elec sented by LiMPO4F ( “ M ” is a transition metal ) such as trolytic solution of the present invention has a high polarity LiFePO4F and borate based compounds represented by and a slightly high viscosity, a film which is easily impreg LIMBOZ ( “ M ” is a transition metal ) such as LiFeBO3 . Any nated with a polar solvent such as water is preferable . metal oxide used as the positive electrode active material 50 Specifically, a film in which 90 % or more of gaps existing may have a basic composition of the composition formulae therein are impregnated with a polar solvent such as water described above , and those in which a metal element is preferable . included in the basic composition is substituted with another An electrode assembly is formed from the positive elec metal element may also be used . trode , the negative electrode , and , if necessary , the separator In addition , as the positive electrode active material, a 55 interposed therebetween . The electrode assembly may be a positive electrode active material that does not include a laminated type obtained by stacking the positive electrode, charge carrier that contributes to charging and discharging the separator, and the negative electrode , or a wound type may be used . For example, in the case with the lithium ion obtained by winding the positive electrode, the separator, secondary battery, elemental substance sulfur ( S ) , a com- and the negative electrode . The nonaqueous electrolyte pound that is a composite of sulfur and carbon , metal 60 secondary battery is preferably formed by respectively con sulfides such as Tisz, oxides such as V205 and MnO2, necting, using current collecting leads or the like , the polyaniline and anthraquinone and compounds including positive electrode current collector to a positive electrode such aromatics in the chemical structure , conjugate based external connection terminal and the negative electrode materials such as conjugate diacetic acid based organic current collector to a negative electrode external connection matters, and other materials known in the art may be used for 65 terminal, and adding the electrolytic solution of the present the positive electrode active material. Furthermore, a com- invention to the electrode assembly. In addition , the non pound having a stable radical such as nitroxide, nitronyl aqueous electrolyte secondary battery of the present inven US 11,011,781 B2 35 36 tion preferably executes charging and discharging at a ( Electrolytic Solution of the Present Invention ) voltage range suitable for the types of active materials ( Electrolytic Solution E1 ) included in the electrodes . The electrolytic solution of the present invention was In the nonaqueous electrolyte secondary battery of the produced in the following manner . present invention including the electrolytic solution of the 5 Approximately 5 mL of 1,2 - dimethoxyethane , which is an present invention , an SEI coating having a special structure organic solvent, was placed in a flask including a stirring bar derived from the electrolytic solution of the present inven and a thermometer . Under a stirring condition , with respect tion is produced on the surface of the negative electrode to 1,2 - dimethoxyethane in the flask , ( CF2SO2 ) 2NLi , which and / or the surface of the positive electrode . As described is a lithium salt , was gradually added so as to maintain a later, the SEI coating includes S and 0 , and has an SO 10 solutiondissolved temperature . Since dissolving equal toof or( CF3S02 lower ) than2NLi 40momentarily ° C. to be structure . Thus, the electrolytic solution of the present stagnated at a time point when approximately 13 8 of invention for producing the SEI coating particularly ( CF3SO2 ) 2NLi was added , the flask was heated by placing includes , in a chemical structure of an anion of the salt , the flask in a temperature controlled bath such that the sulfur element and oxygen element. Hereinafter, if neces 15 solution temperature in the flask reaches 50 ° C. to dissolve sary, the SEI coating which has the special structure is ( CF3S02 ) NLi. Since dissolving of ( CF2SO2 ) , NLi stag referred to as an S , O - containing coating . The S , O - contain nated again at a time point when approximately 15 g of ing coating, in cooperation with the electrolytic solution of ( CF2SO2 ) , NLi was added , a single drop of 1,2 - dimethoxy the present invention , contributes in the improvement of ethane was added thereto using a pipette to dissolve battery characteristics of the nonaqueous electrolyte second- 20 ( CF2SO2 ) ,NLi . Furthermore , (CF2SO2 )2NLi was gradually ary battery improvement of battery life, improvement of added to accomplish adding an entire predetermined amount input - output characteristics, etc. ) . of ( CF2SO2 ) 2NLi . The obtained electrolytic solution was The form of the nonaqueous electrolyte secondary battery transferred to a 20 - mL measuring flask , and 1,2 -dimethoxy of the present invention is not particularly limited , and ethane was added thereto until a volume of 20 mL was various forms such as a cylindrical type, square type , a coin 25 obtained . This was used as electrolytic solution E1 . The type , and a laminated type, etc. , are used . volume of the obtained electrolytic solution was 20 mL , and The nonaqueous electrolyte secondary battery of the 18.38 g of ( CF2SO2 ) 2NLi was contained in the electrolytic solution . The concentration of ( CF2802 ) 2NLi in electrolytic present invention may be mounted on a vehicle . The vehicle solution E1 was 3.2 mol / L . In electrolytic solution E1 , 1.6 may be a vehicle that uses , as all or one portion of the source 30 molecules of 1,2 - dimethoxyethane were contained with of power , electrical energy obtained from the nonaqueous respect to 1 molecule of ( CF2SO2 ) 2NLi . electrolyte secondary battery, and examples thereof include The production was performed within a glovebox under electric vehicles and hybrid vehicles . When the nonaqueous an inert gas atmosphere. electrolyte secondary battery is to be mounted on the ( Electrolytic Solution E2 ) vehicle , a plurality of the nonaqueous electrolyte secondary 35 With a method similar to that of electrolytic solution E1 , batteries may be connected in series to form an assembled electrolytic solution E2 whose concentration of battery. Other than the vehicles , examples of instruments on ( CF2SO2 ) 2NLi was 2.8 mol / L was produced using 16.08 g which the nonaqueous electrolyte secondary battery may be of ( CF2SO2 ) 2NLi . In electrolytic solution E2 , 2.1 molecules mounted include various home appliances, office instru of 1,2 - dimethoxyethane were contained with respect to 1 ments , and industrial instruments driven by a battery such as 40 molecule of ( CF2S02) 2NLi. personal computers and portable communication devices. In ( Electrolytic Solution E3 ) addition , the nonaqueous electrolyte secondary battery of Approximately 5 mL of acetonitrile, which is an organic the present invention may be used as power storage devices solvent, was placed in a flask including a stirring bar. Under and power smoothing devices for wind power generation, a stirring condition , with respect to acetonitrile in the flask , photovoltaic power generation , hydroelectric power genera- 45 ( CF2SO2 ) 2NLi , which is a lithium salt , was gradually added tion , and other power systems , power supply sources for to be dissolved . A total amount of 19.52 g of ( CF3SO2 ) 2NLi auxiliary machineries and / or power of ships , etc. , power was added to the flask , and stirring was performed overnight supply sources for auxiliary machineries and / or power of in the flask . The obtained electrolytic solution was trans aircraft and spacecraft, etc. , auxiliary power supply for ferred to a 20 - mL measuring flask , and acetonitrile was vehicles that do not use electricity as a source of power, 50 added thereto until a volume of 20 mL was obtained . This power supply for movable household robots, power supply was used as electrolytic solution E3 . The production was for system backup, power supply for uninterruptible power performed within a glovebox under an inert gas atmosphere. supply devices, and power storage devices for temporarily The concentration of ( CF2SO2 ) 2NLi in electrolytic solu storing power required for charging at charge stations for tion E3 was 3.4 mol / L . In electrolytic solution E3 , 3 mol electric vehicles . 55 ecules of acetonitrile were contained with respect to 1 Although the embodiments of the present invention have molecule of (CF SO , NLi. been described above , the present invention is not limited to ( Electrolytic Solution E4 ) the embodiments. Without departing from the gist of the With a method similar to that of electrolytic solution E3 , present invention , the present invention can be implemented electrolytic solution E4 whose concentration of in various modes with modifications and improvements, 60 ( CF2S02 ) 2NLi was 4.2 mol / L was produced using 24.11 g of etc. , that can be made by a person skilled in the art . ( CF3S02 ) 2NLi . In electrolytic solution E4 , 1.9 molecules of In the following, embodiments of the present invention acetonitrile were contained with respect to 1 molecule of are described specifically by means of Examples, Compara- (CF SO , ) ,NLi . tive Examples, and the like . The present invention is not ( Electrolytic Solution E5 ) limited to these Examples . Hereinafter, unless mentioned 65 Electrolytic solution E5 whose concentration of otherwise in particular, “ part( s) ” refers to part ( s ) by mass , ( FSO2 ) 2NLi was 3.6 mol / L was produced with a method and “ % ” refers to mass % . similar to that of electrolytic solution E3 except for using US 11,011,781 B2 37 38 13.47 g of ( FSO2) 2NLi as the lithium salt and 1,2 - dime- In electrolytic solution E13 , 3 molecules of dimethyl car thoxyethane as the organic solvent. In electrolytic solution bonate were contained with respect to 1 molecule of E5 , 1.9 molecules of 1,2 - dimethoxyethane were contained ( FSO2 ) ,NLi . with respect to 1 molecule of ( FSO2 ) 2NLi . ( Electrolytic Solution E14 ) ( Electrolytic Solution E6 ) 5 Electrolytic solution E14 whose concentration of With a method similar to that of electrolytic solution E5 , ( FSO2 ) 2NLi was 2.6 mol / L was obtained by adding dimethyl electrolytic solution E6 whose concentration of ( FSO2 ) 2NLi carbonate to , and thereby diluting, electrolytic solution E11 . was 4.0 mol / L was produced using 14.97 g of ( FSO2 ) 2NLi . In electrolytic solution E14 , 3.5 molecules of dimethyl In electrolytic solution E6 , 1.5 molecules of 1,2 - dimethoxy- carbonate were contained with respect to 1 molecule of ethane were contained with respect to 1 molecule of 10 (FSO2 ) 2NLi . (FSO ) ,NLi . ( Electrolytic Solution E15 ) ( Electrolytic Solution E7 ) Electrolytic solution E15 whose concentration Electrolytic solution E7 whose concentration of of ( FSO2 ) 2NLi was 2.0 mol / L was obtained by adding ( FSO2 ) , NLi was 4.2 mol / L was produced with a method 15 dimethyl carbonate to , and thereby diluting, electrolytic similar to that of electrolytic solution E3 except for using solution E11 . In electrolytic solution E15 , 5 molecules of 15.72 g of ( FSO2 ) 2NLi as the lithium salt . In electrolytic dimethyl carbonate were contained with respect to 1 mol solution E7 , 3 molecules of acetonitrile were contained with ecule of ( FSO2 ) 2NLi . respect to 1 molecule of ( FSO2 ) 2NLi . ( Electrolytic Solution E16 ) ( Electrolytic Solution E8 ) 20 Approximately 5 mL of ethyl methyl carbonate, which is With a method similar to that of electrolytic solution E7 , an organic solvent, was placed in a flask including a stirring electrolytic solution E8 whose concentration of ( FSO2 ) 2NLi bar. Under a stirring condition , with respect to ethyl methyl was 4.5 mol / L was produced using 16.83 g of ( FSO2 ) 2NLi . carbonate in the flask , ( FSO2 ) 2NLi , which is a lithium salt , In electrolytic solution E8 , 2.4 molecules of acetonitrile was gradually added to be dissolved . A total amount of 12.81 were contained with respect to 1 molecule of ( FSO2 ) 2NLi . 25 g of ( FSO2 ) 2NLi was added to the flask , and stirring was ( Electrolytic Solution E9 ) performed overnight in the flask . The obtained electrolytic With a method similar to that of electrolytic solution E7 , solution was transferred to a 20 - mL measuring flask , and electrolytic solution E9 whose concentration of ( FSO2 ) 2NLi ethyl methyl carbonate was added thereto until a volume of was 5.0 mol / L was produced using 18.71 g of ( FSO2 ) 2NLii . 20 mL was obtained . This was used as electrolytic solution In electrolytic solution E9 , 2.1 molecules of acetonitrile 30 E16 . The production was performed within a glovebox were contained with respect to 1 molecule of ( FSO2 ) 2NLi . under an inert gas atmosphere . ( Electrolytic Solution E10 ) The concentration of ( FSO2 ) 2NLi in electrolytic solution With a method similar to that of electrolytic solution E7 , E16 was 3.4 mol / L . In electrolytic solution E16 , 2 molecules electrolytic solution E10 whose concentration of of ethyl methyl carbonate were contained with respect to 1 ( FSO2 ) 2NLi was 5.4 mol / L was produced using 20.21 g of 35 molecule of (FSO2 ) 2NLi . ( FSO2 ) 2NLi . In electrolytic solution E10 , 2 molecules of ( Electrolytic Solution E17 ) acetonitrile were contained with respect to 1 molecule of Electrolytic solution E17 whose concentration ( FSO2 ) 2NLi . of ( FSO2 ) 2NLi was 2.9 mol / L was obtained by adding ethyl ( Electrolytic Solution E11 ) 40 methyl carbonate to , and thereby diluting , electrolytic solu Approximately 5 mL of dimethyl carbonate , which is an tion E16 . In electrolytic solution E17 , 2.5 molecules of ethyl organic solvent, was placed in a flask including a stirring bar. methyl carbonate were contained with respect to 1 molecule Under a stirring condition , with respect to dimethyl carbon- of ( FSO2 ) 2NLi . ate in the flask , ( FSO2 ) 2NLi , which is a lithium salt , was ( Electrolytic Solution E18 ) gradually added to be dissolved . A total amount of 14.64 g 45 Electrolytic solution E18 whose concentration of ( FSO2 ) 2NLi was added to the flask , and stirring was of ( FSO2 ) 2NLi was 2.2 mol / L was obtained by adding ethyl performed overnight in the flask . The obtained electrolytic methyl carbonate to , and thereby diluting, electrolytic solu solution was transferred to a 20 - mL measuring flask , and tion E16 . In electrolytic solution E18 , 3.5 molecules of ethyl dimethyl carbonate was added thereto until a volume of 20 methyl carbonate were contained with respect to 1 molecule mL was obtained . This was used as electrolytic solution E11 . 50 of ( FSO2 ) 2NLi . The production was performed within a glovebox under an ( Electrolytic Solution E19 ) inert gas atmosphere . Approximately 5 mL of diethyl carbonate , which is an The concentration of ( FSO2 ) 2NLi in electrolytic solution organic solvent, was placed in a flask including a stirring bar. E11 was 3.9 mol / L . In electrolytic solution E11,2 molecules Under a stirring condition, with respect to diethyl carbonate of dimethyl carbonate were contained with respect to 1 55 in the flask , ( FSO2 ) 2NLi , which is a lithium salt , was molecule of (FSO2 ) ,NLi . gradually added to be dissolved . A total amount of 11.37 g ( Electrolytic Solution E12 ) of ( FSO2 ) 2NLi was added to the flask , and stirring was Electrolytic solution E12 whose concentration of performed overnight in the flask . The obtained electrolytic ( FSO2 ) 2NLi was 3.4 mol / L was obtained by adding dimethyl solution was transferred to a 20 - ml measuring flask , and carbonate to , and thereby diluting , electrolytic solution E11 . 60 diethyl carbonate was added thereto until a volume of 20 mL In electrolytic solution E12 , 2.5 molecules of dimethyl was obtained . This was used as electrolytic solution E19 . carbonate were contained with respect to 1 molecule of The production was performed within a glovebox under an ( FSO2) NLi. inert gas atmosphere . ( Electrolytic Solution E13 ) The concentration of ( FSO2 ) 2NLi in electrolytic solution Electrolytic solution E13 whose concentration of 65 E19 was 3.0 mol / L . In electrolytic solution E19,2 molecules ( FSO2 ) 2NLi was 2.9 mol / L was obtained by adding dimethyl of diethyl carbonate were contained with respect to 1 carbonate to , and thereby diluting , electrolytic solution E11 . molecule of ( FSO2 ) 2NLi . US 11,011,781 B2 39 40 (Electrolytic Solution E20 ) In electrolytic solution C8 , 7 molecules of diethyl carbonate Electrolytic solution E20 whose concentration of were contained with respect to 1 molecule of ( FSO2 ) 2NLi . ( FSO2 ) 2NLi was 2.6 mol / L was obtained by adding diethyl Table 3 shows a list of electrolytic solutions E1 to E21 and carbonate to , and thereby diluting, electrolytic solution E19 . C1 to C8 . In electrolytic solution E20 , 2.5 molecules of diethyl car 5 bonate were contained with respect to 1 molecule TABLE 3 of (FSO2 ) 2NLi. Lithium Organic solvent/ ( Electrolytic Solution E21 ) Lithium Organic salt concentration Lithium salt Electrolytic solution E21 whose concentration of salt solvent ( mol / L ) ( mol ratio ) ( FSO2 ) 2NLi was 2.0 mol / L was obtained by adding diethyl 10 E1 LiTFSA DME 3.2 1.6 carbonate to , and thereby diluting, electrolytic solution E19 . E2 LiTFSA DME 2.8 2.1 In electrolytic solution E21 , 3.5 molecules of diethyl car E3 LiTFSA AN 3.4 3 bonate were contained with respect to 1 molecule of E4 LiTFSA AN 4.2 1.9 ( FSO2 ) 2NLi . E5 LiFSA DME 3.6 1.9 15 E6 LiFSA DME 4.0 1.5 ( Electrolytic Solution C1 ) E7 LiFSA AN 4.2 3 Electrolytic solution Ci whose concentration of E8 LiFSA AN 4.5 2.4 ( CF2SO2 ) 2NLi was 1.0 mol / L was produced with a method E9 LiFSA AN 5.0 2.1 similar to that of electrolytic solution E3 , except for using E10 LiFSA AN 5.4 2 E11 LiFSA DMC 3.9 2 5.74 g of ( CF3S02 ) 2NLi and 1,2 - dimethoxyethane as the E12 LiFSA DMC 3.4 2.5 organic solvent. In electrolytic solution C1 , 8.3 molecules of 20 E13 LiFSA DMC 2.9 3 1,2 -dimethoxyethane were contained with respect to 1 mol E14 LiFSA DMC 2.6 3.5 E15 LiFSA DMC 2.0 5 ecule of ( CF3SO2 ) 2NLi . E16 LiFSA EMC 3.4 2 ( Electrolytic Solution C2 ) E17 LiFSA EMC 2.9 2.5 With a method similar to that of electrolytic solution E3 , E18 LiFSA EMC 2.2 3.5 electrolytic solution C2 whose concentration 25 E19 LiFSA DEC 3.0 2 E20 LiFSA DEC 2.6 2.5 of ( CF3S02 ) 2NLi was 1.0 mol / L was produced using 5.74 g E21 LiFSA DEC 2.0 3.5 of ( CF2SO2 ) 2NLi . In electrolytic solution C2 , 16 molecules C1 LiTFSA DME 1.0 8.3 of acetonitrile were contained with respect to 1 molecule of LiTFSA AN 1.0 16 ( CF2SO2) 2NLi. LiFSA DME 1.0 8.8 ( Electrolytic Solution C3 ) 30 LiFSA AN 1.0 17 LiPF EC / DEC 1.0 With a method similar to that of electrolytic solution E5 , C6 LiFSA DMC 1.1 10 electrolytic solution C3 whose concentration of ( FSO2 ) 2NLi C7 LiFSA EMC 1.1 8 was 1.0 mol / L was produced using 3.74 g of (FSO2 ) 2NLi. In C8 LiFSA DEC 1.1 7 electrolytic solution C3 , 8.8 molecules of 1,2 - dimethoxy LiTFSA : ( CF3SO2) 2NLi, ethane were contained with respect to 1 molecule 35 LiFSA : ( FSO2) 2NLi of ( FSO2 ) 2NLi . AN : acetonitrile , ( Electrolytic Solution C4 ) DME : 1,2 -dimethoxyethane With a method similar to that of electrolytic solution E7 , DMC : dimethyl carbonate , electrolytic solution C4 whose concentration of ( FSO2 ) 2NLi EMC : ethyl methyl carbonate , was 1.0 mol / L was produced using 3.74 g of (FSO2 ) 2NLi. In 40 ECDEC / : DECdiethyl : Mixed carbonate solvent of ethylene carbonate and diethyl carbonate ( volume ratio 3 : 7 ) electrolytic solution C4 , 17 molecules of acetonitrile were contained with respect to 1 molecule of ( FSO2 ) 2NLi . ( Electrolytic Solution C5 ) Evaluation Example 1 : IR Measurement Electrolytic solution C5 whose concentration of LiPF . was 1.0 mol / L was produced with a method similar to that 45 ditionsIR measurement on electrolytic was solutions performed E3 , usingE4 , E7 the, E8 following, E10, C2 ,con and of electrolytic solution E3 except for using a mixed solvent C4 , acetonitrile, ( CF2SO2 ) 2NLi , and ( FSO2 ) 2NLi . An IR of ethylene carbonate and diethyl carbonate ( volume ratio of spectrum in a range of 2100 to 2400 cm - t is shown in each 3 : 7 ; hereinafter, sometimes referred to as “ EC /DEC ” ) as the of FIGS . 1 to 10. Furthermore , IR measurement was per organic solvent, and 3.04 g of LiPF , as the lithium salt . formed using the following conditions on electrolytic solu ( Electrolytic Solution C6 ) 50 tions E11 to E21 and C6 to C8 , dimethyl carbonate , ethyl Electrolytic solution C6 whose concentration methyl carbonate , and diethyl carbonate . An IR spectrum in of ( FSO2 ) 2NLi was 1.1 mol / L was obtained by adding a range of 1900 to 1600 cm- ' is shown in each of FIGS . 11 dimethyl carbonate to , and thereby diluting , electrolytic to 27. In addition , an IR spectrum of ( FSO2 ) 2NLi in a range solution E11 . In electrolytic solution C6 , 10 molecules of of 1900 to 1600 cm- ' is shown in FIG . 28. In each figure, the dimethyl carbonate were contained with respect to 1 mol- 55 horizontal axis represents wave number ( cm - 1 ) and the ecule of ( FSO ) , NLi. vertical axis represents absorbance ( reflective absorbance ). ( Electrolytic Solution C7 ) IR Measuring Conditions Electrolytic solution C7 whose concentration Device : FT - IR (manufactured by Bruker Optics K.K. ) of ( FSO2 ) 2NLi was 1.1 mol / L was obtained by adding ethyl Measuring condition : ATR method ( diamond was used ) methyl carbonate to , and thereby diluting , electrolytic solu- 60 Measurement atmosphere: Inert gas atmosphere tion E16 . In electrolytic solution C7 , 8 molecules of ethyl At around 2250 cm - l in the IR spectrum of acetonitrile methyl carbonate were contained with respect to 1 molecule shown in FIG . 8 , a characteristic peak derived from stretch of (FSO ) NLi. ing vibration of a triple bond between C and N of acetonitrile ( Electrolytic Solution C8 ) was observed. No particular peaks were observed at around Electrolytic solution C8 whose concentration of 65 2250 cm in the IR spectrum of ( CF2SO2 ) 2NLi shown in ( FSO2 ) 2NLi was 1.1 mol / L was obtained by adding diethyl FIG . 9 and the IR spectrum of ( FSO2 ) 2NLi shown in FIG . carbonate to , and thereby diluting, electrolytic solution E19 . 10 . US 11,011,781 B2 41 42 In the IR spectrum of electrolytic solution E3 shown in observed at around 1750 cm- ?. No particular peaks were FIG . 1 , a characteristic peak derived from stretching vibra- observed at around 1750 cm ? in the IR spectrum tion of a triple bond between C and N of acetonitrile was of ( FSO2 ) 2NLi shown in FIG . 28 . slightly ( Io = 0.00699 ) observed at around 2250 cm- ?. Addi- In the IR spectrum of electrolytic solution E11 shown in tionally in the IR spectrum in FIG . 1 , a characteristic peak 5 FIG . 11 , a characteristic peak derived from stretching vibra derived from stretching vibration of a triple bond between C tion of a double bond between C and O of dimethyl and N of acetonitrile was observed at a peak intensity of carbonate was slightly ( Io = 0.16628 ) observed at around Is = 0.05828 at around 2280 cm -1 shifted toward the high 1750 cm- ' . Additionally in the IR spectrum in FIG . 11 , a wave number side from around 2250 cm- ?. The relationship characteristic peak derived from stretching vibration of a between peak intensities of Is and Io was Is > Io and Is = 8xlo . 10 double bond between C and O of dimethyl carbonate was In the IR spectrum of electrolytic solution E4 shown in observed at a peak intensity of Is = 0.48032 at around 1717 FIG . 2 , a peak derived from acetonitrile was not observed at cm - 1 shifted toward the low wave number side from around around 2250 cm - l , whereas a characteristic peak derived 1750 cm- ?. The relationship between peak intensities of Is from stretching vibration of a triple bond between C and N and Io was Is > lo and Is = 2.89xlo . of acetonitrile was observed at a peak intensity of 15 In the IR spectrum of electrolytic solution E12 shown in Is = 0.05234 at around 2280 cm- ? shifted toward the high FIG . 12 , a characteristic peak derived from stretching vibra wave number side from around 2250 cm - 1 . The relationship tion of a double bond between C and O of dimethyl between peak intensities of Is and Io was Is > Io . carbonate was slightly ( lo - 0.18129 ) observed at around In the IR spectrum of electrolytic solution E7 shown in 20 1750 cm - . Additionally in the IR spectrum in FIG . 12 , a FIG . 3 , a characteristic peak derived from stretching vibra- characteristic peak derived from stretching vibration of a tion of a triple bond between C and N of acetonitrile was double bond between C and O of dimethyl carbonate was slightly ( lo = 0.00997 ) observed at around 2250 cm - 7 . Addi- observed at a peak intensity of Is = 0.52005 at around 1717 tionally in the IR spectrum in FIG . 3 , a characteristic peak cm - 1 shifted toward the low wave number side from around derived from stretching vibration of a triple bond between C 25 1750 cm- ' . The relationship between peak intensities of Is and N of acetonitrile was observed at a peak intensity of and Io was Is > lo and Is = 2.87xIo . Is = 0.08288 at around 2280 cm -1 shifted toward the high In the IR spectrum of electrolytic solution E13 shown in wave number side from around 2250 cm- !. The relationship FIG . 13 , a characteristic peak derived from stretching vibra between peak intensities of Is and Io was Is > Io and Is = 8x1o . tion of a double bond between C and O of dimethyl A peak having a similar intensity and similar wave number 30 carbonate was slightly ( Io = 0.20293 ) observed at around to those in the IR chart of FIG . 3 was also observed in the 1750 cm - . Additionally in the IR spectrum in FIG . 13 , a IR spectrum of electrolytic solution E8 shown in FIG . 4. The characteristic peak derived from stretching vibration of a relationship between peak intensities of Is and Io was Is > Io double bond between C and O of dimethyl carbonate was and Is = 11xlo . observed at a peak intensity of Is = 0.53091 at around 1717 In the IR spectrum of electrolytic solution E10 shown in 35 cm- shifted toward the low wave number side from around FIG . 5 , a peak derived from acetonitrile was not observed at 1750 cm- ?. The relationship between peak intensities of Is around 2250 cm- ?, whereas a characteristic peak derived and Io was Is > Io and Is = 2.62xIo . from stretching vibration of a triple bond between C and N In the IR spectrum of electrolytic solution E14 shown in of acetonitrile was observed at a peak intensity of FIG . 14 , a characteristic peak derived from stretching vibra Is = 0.07350 at around 2280 cm- shifted toward the high 40 tion of a double bond between C and O of dimethyl wave number side from around 2250 cm - 1 . The relationship carbonate was slightly ( Io = 0.23891 ) observed at around between peak intensities of Is and Io was Is > Io . 1750 cm - 7 . Additionally in the IR spectrum in FIG . 14 , a In the IR spectrum of electrolytic solution C2 shown in characteristic peak derived from stretching vibration of a FIG . 6 , a characteristic peak derived from stretching vibra- double bond between C and O of dimethyl carbonate was tion of a triple bond between C and N of acetonitrile was 45 observed at a peak intensity of Is = 0.53098 at around 1717 observed at a peak intensity of Io = 0.04441 at around 2250 cm - 1 shifted toward the low wave number side from around cm- in a manner similar to FIG . 8. Additionally in the IR 1750 cm - 7 . The relationship between peak intensities of Is spectrum in FIG . 6 , a characteristic peak derived from and Io was Is > lo and Is = 2.22xlo . stretching vibration of a triple bond between C and N of In the IR spectrum of electrolytic solution E15 shown in acetonitrile was observed at a peak intensity of Is = 0.03018 50 FIG . 15 , a characteristic peak derived from stretching vibra at around 2280 cm- shifted toward the high wave number tion of a double bond between C and O of dimethyl side from around 2250 cm - 1. The relationship between peak carbonate was slightly ( Io - 0.30514 ) observed at around intensities of Is and Io was Is < Io . 1750 cm - 7 . Additionally in the IR spectrum in FIG . 15 , a In the IR spectrum of electrolytic solution C4 shown in characteristic peak derived from stretching vibration of a FIG . 7 , a characteristic peak derived from stretching vibra- 55 double bond between C and 0 of dimethyl carbonate was tion of a triple bond between C and N of acetonitrile was observed at a peak intensity of Is = 0.50223 at around 1717 observed at a peak intensity of Io = 0.04975 at around 2250 cm - 1 shifted toward the low wave number side from around cm- in a manner similar to FIG . 8. Additionally in the IR 1750 cm - 7 . The relationship between peak intensities of Is spectrum in FIG . 7 , a characteristic peak derived from and lo was Is > lo and Is = 1.65xlo . stretching vibration of a triple bond between C and N of 60 In the IR spectrum of electrolytic solution C6 shown in acetonitrile was observed at a peak intensity of Is = 0.03804 FIG . 22 , a characteristic peak derived from stretching vibra at around 2280 cm- shifted toward the high wave number tion of a double bond between C and O of dimethyl side from around 2250 cm - 1 . The relationship between peak carbonate was observed ( Io = 0.48204 ) at around 1750 cm- ' . intensities of Is and lo was Is < Io . Additionally in the IR spectrum in FIG . 22 , a characteristic In the IR spectrum of dimethyl carbonate shown in FIG . 65 peak derived from stretching vibration of a double bond 25 , a characteristic peak derived from stretching vibration of between C and O of dimethyl carbonate was observed at a a double bond between C and O of dimethyl carbonate was peak intensity of Is = 0.39244 at around 1717 cm - 1 shifted US 11,011,781 B2 43 44 toward the low wave number side from around 1750 cm - 1 . In the IR spectrum of electrolytic solution E20 shown in The relationship between peak intensities of Is and Io was FIG . 20 , a characteristic peak derived from stretching vibra Is Io . tion of a double bond between C and O of diethyl carbonate At around 1745 cm -1 in the IR spectrum of ethyl methyl was slightly ( Io = 0.15231 ) observed at around 1742 cm - 1 . carbonate shown in FIG . 26 , a characteristic peak derived 5 Additionally in the IR spectrum in FIG . 20 , a characteristic from stretching vibration of a double bond between C and O peak derived from stretching vibration of a double bond between C and O of diethyl carbonate was observed at a of ethyl methyl carbonate was observed . peak intensity of Is = 0.45679 at around 1706 cm- ? shifted In the IR spectrum of electrolytic solution E16 shown in toward the low wave number side from around 1742 cm - 1 . FIG . 16 , a characteristic peak derived from stretching vibra 10 The relationship between peak intensities of Is and Io was tion of a double bond between C and O of ethyl methyl Is > lo and Is = 3.00xIo . carbonate was slightly ( Io - 0.13582 ) observed at around In the IR spectrum of electrolytic solution E21 shown in 1745 cm- ?. Additionally in the IR spectrum in FIG . 16 , a FIG . 21 , a characteristic peak derived from stretching vibra characteristic peak derived from stretching vibration of a tion of a double bond between C and 0 of diethyl carbonate double bond between Cand 0 of ethyl methyl carbonate was 15 was slightly ( Io = 0.20337 ) observed at around 1742 cm- ?. observed at a peak intensity of Is = 0.45888 at around 1711 Additionally in the IR spectrum in FIG . 21 , a characteristic cm - 1 shifted toward the low wave number side from around peak derived from stretching vibration of a double bond 1745 cm - 7 . The relationship between peak intensities of Is between C and O of diethyl carbonate was observed at a and Io was Is > Io and Is = 3.38xlo . peak intensity of Is = 0.43841 at around 1706 cm- shifted In the IR spectrum of electrolytic solution E17 shown in 20 toward the low wave number side from around 1742 cm - 1 . FIG . 17 , a characteristic peak derived from stretching vibra- The relationship between peak intensities of Is and lo was tion of a double bond between C and O of ethyl methyl Is > lo and Is = 2.16xlo . carbonate was slightly ( Io - 0.15151 ) observed at around In the IR spectrum of electrolytic solution C8 shown in 1745 cm- ?. Additionally in the IR spectrum in FIG . 17 , a FIG . 24 , a characteristic peak derived from stretching vibra characteristic peak derived from stretching vibration of a 25 tion of a double bond between C and 0 of diethyl carbonate double bond between C and 0 of ethyl methyl carbonate was was observed ( Io = 0.39636 ) at around 1742 cm - 1 . Addition observed at a peak intensity of Is = 0.48779 at around 1711 ally in the IR spectrum in FIG . 24 , a characteristic peak cm - 1 shifted toward the low wave number side from around derived from stretching vibration of a double bond between 1745 cm - 1 . The relationship between peak intensities of Is C and O of diethyl carbonate was observed at a peak and Io was Is > lo and Is = 3.22xlo . 30 intensity of Is = 0.31129 at around 1709 cm- shifted toward In the IR spectrum of electrolytic solution E18 shown in the low wave number side from around 1742 cm - 1 . The FIG . 18 , a characteristic peak derived from stretching vibra- relationship between peak intensities of Is and Io was Is < lo . tion of a double bond between C and O of ethyl methyl carbonate was slightly ( lo = 0.20191 ) observed at around Evaluation Example 2 : Ionic Conductivity 1745 cm-?. Additionally in the IR spectrum in FIG . 18 , a 35 characteristic peak derived from stretching vibration of a Ionic conductivities of electrolytic solutions E1 , E2 , E4 to double bond between C and 0 of ethyl methyl carbonate was E6 , E8 , E11 , E16 , and E19 were measured using the observed at a peak intensity of Is = 0.48407 at around 1711 following conditions . The results are shown in Table 4 . cm - 1 shifted toward the low wave number side from around Ionic Conductivity Measuring Conditions 1745 cm - 1 . The relationship between peak intensities of Is 40 Under an Ar atmosphere, an electrolytic solution was and Io was Is > Io and Is = 2.40xIo . sealed in a glass cell that has a platinum electrode and whose In the IR spectrum of electrolytic solution C7 shown in cell constant is known , and impedance thereof was mea FIG . 23 , a characteristic peak derived from stretching vibra- sured at 30 ° C. , 1 kHz . Ionic conductivity was calculated tion of a double bond between C and O of ethyl methyl based on the result of measuring impedance . As a measure carbonate was observed ( Io = 0.41907 ) at around 1745 cm - 1 . 45 ment instrument, Solartron 147055BEC ( Solartron Analyti Additionally in the IR spectrum in FIG . 23 , a characteristic cal) was used . peak derived from stretching vibration of a double bond between C and 0 of ethyl methyl carbonate was observed at TABLE 4 a peak intensity of Is = 0.33929 at around 1711 cm - shifted Ionic toward the low wave number side from around 1745 cm- ?. 50 Organic Lithium salt concentration conductivity The relationship between peak intensities of Is and Io was Lithium salt solvent (mol / L ) ( mS / cm - 1 ) Is < lo . 1 E1 LiTFSA DME 3.2 2.4 At around 1742 cm in the IR spectrum of diethyl E2 LiTFSA DME 2.8 4.4 carbonate shown in FIG . 27 , a characteristic peak derived E4 LiTFSA AN 4.2 1.0 from stretching vibration of a double bond between C and 0 55 E5 LiFSA DME 3.6 7.2 E6 LiFSA DME 4.0 7.1 of diethyl carbonate was observed . E8 LiFSA AN 4.5 9.7 In the IR spectrum of electrolytic solution E19 shown in E9 LiFSA AN 5.0 7.5 FIG . 19 , a characteristic peak derived from stretching vibra E11 LiFSA DMC 3.9 2.3 tion of a double bond between C and O of diethyl carbonate E13 LiFSA DMC 2.9 4.6 was slightly ( lo = 0.11202 ) observed at around 1742 cm - 1 . 60 E16 LiFSA EMC 3.4 1.8 Additionally in the IR spectrum in FIG . 19 , a characteristic E19 LiFSA DEC 3.0 1.4 peak derived from stretching vibration of a double bond between C and O of diethyl carbonate was observed at a Electrolytic solutions E1 , E2 , E4 to E6 , E8 , E11 , E16 , and peak intensity of Is = 0.42925 at around 1706 cm- ? shifted E19 all displayed ionic conductivity. Thus, the electrolytic toward the low wave number side from around 1742 cm- ?. 65 solutions of the present invention are understood to be all The relationship between peak intensities of Is and Io was capable of functioning as electrolytic solutions of various Is > lo and Is = 3.83xlo . batteries . US 11,011,781 B2 45 46 Evaluation Example 3 : Viscosity Maximum volatilization rates of electrolytic solutions E2 , E4 , E8 , E11 , and E13 were significantly smaller than maxi Viscosities of electrolytic solutions E1 , E2 , E4 to E6 , E8 , mum volatilization rates of electrolytic solutions Ci , C2 , E11 , E16 , E19 , C1 to C4 , and C6 to C8 were measured using C4 , and C6 . Thus, even if a battery using the electrolytic the following conditions. The results are shown in Table 5. 5 solution of the present invention is damaged , rapid volatil Viscosity Measuring Conditions ization of the organic solvent outside the battery is sup Under an Ar atmosphere , an electrolytic solution was pressed since the volatilization rate of the electrolytic solu sealed in a test cell , and viscosity thereof was measured tion is small . under a condition of 30 ° C. by using a falling ball viscometer ( Louis 2000 M manufactured by Anton Paar GmbH ). 10 Evaluation Example 5 : Combustibility TABLE 5 Combustibility of electrolytic solutions E4 and C2 was tested using the following method . Lithium salt Viscosity Three drops of an electrolytic solution were dropped on a Lithium salt Organic solvent concentration (mol / L ) ( mPa · s ) 15 glass filter by using a pipette to have the electrolytic solution E1 LiTFSA DME 3.2 36.6 E2 LiTFSA DME 2.8 31.6 retained by the glass filter. The glass filter was held by a pair E4 LiTFSA AN 4.2 138.0 of tweezers, and the glass filter was brought in contact with E5 LiFSA DME 3.6 25.1 a flame. E6 4.0 LiFSA DME 30.3 20 Electrolytic solution E4 did not ignite even when being E8 LiFSA AN 4.5 23.8 E9 LiFSA AN 5.0 31.5 brought in contact with a flame for 15 seconds. On the other E11 LiFSA DMC 3.9 34.2 hand, electrolytic solution C2 burned out in a little over 5 E13 LiFSA DMC 2.9 17.6 E16 LiFSA EMC 3.4 29.7 seconds . Thus, the electrolytic solution of the present inven E19 LiFSA DEC 3.0 23.2 tion was confirmed to be unlikely to combust. C1 LiTFSA DME 1.0 1.3 25 C2 LiTFSA AN 1.0 0.75 Evaluation Example 6 : Low Temperature Test C3 LiFSA DME 1.0 1.2 C4 LiFSA AN 1.0 0.74 C6 LiFSA DMC 1.1 1.38 Electrolytic solutions E11 , E13 , E16 , and E19 were each C7 LiFSA EMC 1.1 1.67 placed in a container, and the container was filled with inert C8 LiFSA DEC 1.1 2.05 30 gas and sealed . These solutions were stored in a -30 ° C. freezer for two days. Each of the electrolytic solutions after When compared to the viscosities of electrolytic solutions storage was observed . All of the electrolytic solutions main C1 to C4 and C6 to C8 , the viscosities of electrolytic tained a liquid state without solidifying, and depositing of solutions E1 , E2 , E4 to E6 , E8 , E11 , E16 , and E19 were salts was also not observed . significantly higher. Thus, with a battery using the electro 35 lytic solution of the present invention , even if the battery is Evaluation Example 7 : Raman Spectrum damaged , leakage of the electrolytic solution is suppressed . Measurement Raman spectrum measurement was performed on elec Evaluation Example 4 : Volatility 40 trolytic solutions E8 , E9 , C4 , E11 , E13 , E15 , and C6 using the following conditions. FIGS . 29 to 35 each show a Raman Volatilities of electrolytic solutions E2 , E4 , E8 , E11 , E13 , spectrum in which a peak derived from an anion portion of C1 , C2 , C4 , and C6 were measured sing the following a metal salt of an electrolytic solution was observed . In each method . of the figures, the horizontal axis represents wave number Approximately 10 mg of an electrolytic solution was 45 ( cm- ? ) and the vertical axis represents scattering intensity. placed in a pan made from aluminum , and the pan was Raman Spectrum Measurement Conditions disposed in a thermogravimetry measuring device ( SDT600 Device : Laser Raman spectrometer ( NRS series, JASCO manufactured by TA Instruments ) to measure weight change Corp.) of the electrolytic solution at room temperature . Volatiliza- Laser wavelength : 532 nm tion rate was calculated through differentiation of weight 50 The electrolytic solutions were each sealed in a quartz cell change ( mass % ) by time . Among the obtained volatilization under an inert gas atmosphere and subjected to the mea rates, largest values were selected and are shown in Table 6 . surement. In electrolytic solutions E8 , E9 , and C4 shown in FIGS . TABLE 6 29 to 31 , at 700 to 800 cm - l in the Raman spectra , charac 55 teristic peaks derived from ( FSO2 ) 2N of LiFSA dissolved in Maximum Lithium Organic Lithium salt concentration volatilization rate acetonitrile were observed . Here, based on FIGS . 29 to 31 , salt solvent (mol / L ) (mass % /min .) the peak is understood as to shift toward the high wave number side associated with an increase in the concentration E2 LiTFSA DME 2.8 0.4 E4 LiTFSA AN 4.2 2.1 of LiFSA . As the concentration of the electrolytic solution ES LiFSA AN 4.5 0.6 60 becomes higher, ( FSO2 ) 2N corresponding to the anion of a E11 LiFSA DMC 3.9 0.1 salt is speculated to enter of state of interacting with Li . In E13 LiFSA DMC 2.9 1.3 other words , Li and an anion are speculated to mainly form LiTFSA DME 1.0 9.6 LiTFSA AN 1.0 13.8 an SSIP ( Solvent- separated ion pairs ) state at a low concen LiFSA AN 1.0 16.3 tration , and mainly forma CIP ( Contact ion pairs ) state or an LiFSA DMC 1.1 6.1 65 AGG ( aggregate ) state as the concentration becomes higher . 5888 Such a state is thought to be observed as a peak shift in the Raman spectrum . US 11,011,781 B2 47 48 In electrolytic solutions E11 , E13 , E15 , and C6 shown in electrolytic solution of the present invention is regarded as FIGS . 32 to 35 , at 700 to 800 cm -1 in the Raman spectra , to maintain a liquid state even at a low temperature . characteristic peaks derived from ( FSO2 ) 2N of LiFSA dis- The following specific electrolytic solutions are provided solved in dimethyl carbonate were observed . Here , based on as the electrolytic solution of the present invention . The FIGS . 32 to 35 , the peak is understood as to shift toward the 5 following electrolytic solutions also include those previ high wave number side associated with an increase in the ously stated . concentration of LiFSA . As considered in the previous ( Electrolytic Solution A ) paragraph , this phenomenon is speculated to be a result of a The electrolytic solution of the present invention was state , in which ( FSO2 ) 2N corresponding to the anion of a salt produced in the following manner . is interacting with multiple Li ions , being reflected in the 10 Approximately 5 mL of 1,2 -dimethoxyethane , which is an spectrum , as the concentration of the electrolytic solution organic solvent, was placed in a flask including a stirring bar became higher. and a thermometer. Under a stirring condition , with respect Evaluation Example 8 : Li Transference Number to 1,2 - dimethoxyethane in the flask , (CF SO2 ) NLi, which 15 is a lithium salt , was gradually added so as to maintain a Li transference numbers of electrolytic solutions E2 , E8 , solution temperature equal to or lower than 40 ° C. to be C4 , and C5 were measured using the following conditions . dissolved . Since dissolving of ( CF SO2) 2NLi momentarily An NMR tube including one of the electrolytic solutions stagnated at a time point when approximately 13 g of was placed in a PFG - NMR device ( ECA - 500 , JEOL Ltd. ) , ( CF3SO2 ) 2NLi was added, the flask was heated by placing and diffusion coefficients of Li ions and anions in each of the 20 the flask in a temperature controlled bath such that the electrolytic solutions were measured on ' Li and 1 ° F as solution temperature in the flask reaches 50 ° C. to dissolve targets at a condition of 500 MHz and magnetic field ( CF2SO2 ) 2NLi . Since dissolving of ( CF2SO2 ) 2NLi stag gradient of 1.26 T / m while altering a magnetic field pulse nated again at a time point when approximately 15 g of width , using spin echo method . The Li transference number (CF SO2) NLi was added , a single drop of 1,2 - dimethoxy was calculated from the following formula . 25 ethane was added thereto using a pipette to dissolve Li transference number = ( Li ionic diffusion coeffi ( CF2SO2 ) , NLi. Furthermore , ( CF SO2) 2NLi was gradually cient ) / (Li ionic diffusion coefficient + anion diffu added to accomplish adding an entire predetermined amount sion coefficient) of ( CF2SO2 ) 2NLi . The obtained electrolytic solution was The results of the measurement of Li transference num- transferred to a 20 - mL measuring flask , and 1,2 -dimethoxy bers are shown in Table 7 . 30 ethane was added thereto until a volume of 20 mL was obtained . The volume of the obtained electrolytic solution was 20 mL , and 18.38 g of ( CF2SO2 ) 2NLi was contained in TABLE 7 the electrolytic solution . This was used as electrolytic solu Organic Lithium salt Li transference tion A. In electrolytic solution A , the concentration of Lithium salt solvent concentration ( mol / L ) number 35 ( CF2SO2 ) 2NLi was 3.2 mol / L and the density was 1.39 E2 LiTFSA DME 2.8 0.52 g / cmº . The density was measured at 20 ° C. E8 LiFSA AN 4.5 0.50 The production was performed within a glovebox under C4 LiFSA AN 1.0 0.42 an inert gas atmosphere . C5 LiPF EC / DEC 1.0 0.40 ( Electrolytic Solution B ) 40 With a method similar to that of electrolytic solution A , When compared to the Li transference numbers of elec- electrolytic solution whose concentration of trolytic solutions C4 and C5 , the Li transference numbers of ( CF2SO2 ) 2NLi was 2.8 mol / L and whose density was 1.36 electrolytic solutions E2 and E8 were significantly higher. g / cm² was produced . Here, Li ionic conductivity of an electrolytic solution is ( Electrolytic Solution C ) calculated by multiplying ionic conductivity ( total ionic 45 Approximately 5 mL of acetonitrile, which is an organic conductivity ) of the electrolytic solution by the Li transfer- solvent, was placed in a flask including a stirring bar. Under ence number. As a result , when compared to a conventional a stirring condition , with respect to acetonitrile in the flask , electrolytic solution having about the same level of ionic ( CF3S02 ) 2NLi , which is a lithium salt , was gradually added conductivity , the electrolytic solution of the present inven- to be dissolved . A predetermined amount of ( CF2SO2 ) 2NLi tion shows a high transportation rate of lithium ion ( cation ). 50 was added to the flask , and stirring was performed overnight In addition , the Li transference number when the tem- in the flask . The obtained electrolytic solution was trans perature was altered was measured in the electrolytic solu- ferred to a 20 - mL measuring flask , and acetonitrile was tion E8 in accordance with the measuring conditions for the added thereto until a volume of 20 mL was obtained . This above described Li transference numbers . The results are was used as electrolytic solution C. The production was shown in Table 8 . 55 performed within a glovebox under an inert gas atmosphere. Electrolytic solution C contained ( CF3S02 ) 2NLi at a TABLE 8 concentration of 4.2 mol / L , and had a density of 1.52 g / cmº . ( Electrolytic Solution D ) Temperature ( ° C. ) Li transference number With a method similar to that of electrolytic solution C , 30 0.50 60 electrolytic solution D whose concentration of 10 0.50 ( CF3802 ) 2NLi was 3.0 mol / L and whose density was 1.31 -10 0.50 g / cmº was produced . -30 0.52 ( Electrolytic Solution E ) With a method similar to that of electrolytic solution C Based on the results in Table 8 , the electrolytic solution of 65 except for using sulfolane as the organic solvent, electrolytic the present invention is understood as to maintain a suitable solution E whose concentration of ( CF3S02 ) 2NLi was 3.0 Li transference number regardless of the temperature. The mol / L and whose density was 1.57 g / cm3 was produced . US 11,011,781 B2 49 50 ( Electrolytic Solution F ) The concentration of ( FSO2 ) 2NLi in electrolytic solution With a method similar to that of electrolytic solution C N was 3.4 mol / L , and the density of electrolytic solution N except for using dimethyl sulfoxide as the organic solvent, was 1.35 g / cm3. electrolytic solution F whose concentration of (Electrolytic Solution O) ( CF2SO2 ) 2NLi was 3.2 mol / L and whose density was 1.49 5 Approximately 5 mL of diethyl carbonate, which is an g/ cm was produced . organic solvent, was placed in a flask including a stirring bar . ( Electrolytic Solution G ) Under a stirring condition, with respect to diethyl carbonate With a method similar to that of electrolytic solution C in the flask , ( FSO2 ) 2NLi , which is a lithium salt , was except for using ( FSO2 ) 2NLi as the lithium salt and using gradually added to be dissolved . A total amount of 11.37 g 1,2 - dimethoxyethane as the organic solvent, electrolytic 10 of ( FSO2 ) 2NLi was added to the flask , and stirring was solution G whose concentration of ( FSO2 ) 2NLi was 4.0 performed overnight in the flask . The obtained electrolytic mol/ L and whose density was 1.33 g / cm was produced. solution was transferred to a 20 - mL measuring flask , and (Electrolytic Solution H ) diethyl carbonate was added thereto until a volume of 20 mL With a method similar to that of electrolytic solution G , 15 was obtained . This was used as electrolytic solution 0. The electrolytic solution H whose concentration of ( FSO2 ) 2NLi production was performed within a glovebox under an inert was 3.6 mol / L and whose density was 1.29 g / cm was gas atmosphere . produced. The concentration of (FSO2 ) NLi in electrolytic solution (Electrolytic Solution I ) O was 3.0 mol / L , and the density of electrolytic solution O With a method similar to that of electrolytic solution G , 20 was 1.29 g / cm . electrolytic solution I whose concentration of (FSO2 ) 2NLi Table 9 shows a list of the electrolytic solutions described was 2.4 mol / L and whose density was 1.18 g / cm was above . produced . ( Electrolytic Solution J ) TABLE 9 With a method similar to that of electrolytic solution G 25 except for using acetonitrile as the organic solvent, electro Lithium salt Organic solvent Density d ( g /cm ) lytic solution J whose concentration of ( FSO2 ) 2NLi was 5.0 Electrolytic solution A LITFSA DME 1.39 mol / L and whose density was 1.40 g / cm was produced . Electrolytic solution B LiTFSA DME 1.36 Electrolytic solution C LiTFSA AN 1.52 ( Electrolytic Solution K ) Electrolytic solution D LiTFSA AN 1.31 With a method similar to that of electrolytic solution J , 30 Electrolytic solution E LITFSA SL 1.57 electrolytic solution K whose concentration of ( FSO2 ) 2NLi Electrolytic solution F LITFSA DMSO 1.49 was 4.5 mol / L and whose density was 1.34 g /cm was Electrolytic solution G LiFSA DME 1.33 produced . Electrolytic solution H LiFSA DME 1.29 Electrolytic solution I LiFSA DME 1.18 ( Electrolytic Solution L ) Electrolytic solution J LiFSA AN 1.40 Approximately 5 mL of dimethyl carbonate, which is an 35 Electrolytic solution K LiFSA AN 1.34 organic solvent, was placed in a flask including a stirring bar. Electrolytic solution L LiFSA DMC 1.44 Under a stirring condition, with respect to dimethyl carbon- Electrolytic solution M LiFSA DMC 1.36 ate in the flask , ( FSO2 ) 2NLi , which is a lithium salt , was Electrolytic solution N LiFSA EMC 1.35 gradually added to be dissolved . A total amount of 14.64 g Electrolytic solution | LiFSA DEC 1.29 of ( FSO2 ) 2NLi was added to the flask , and stirring was 40 LiFSALiTFSA : (:FSO2 ( CF3SO2) 2NLi )2NLi, , performed overnight in the flask . The obtained electrolytic AN : acetonitrile, solution was transferred to a 20 - ml measuring flask , and DME : 1,2 - dimethoxyethane , dimethyl carbonate was added thereto until a volume of 20 DMSO : dimethyl sulfoxide, mL was obtained . This was used as electrolytic solution L. SL : sulfolane, The production was performed within a glovebox under an 45 DMC: dimethyl carbonate, inert gas atmosphere . EMC : ethyl methyl carbonate , The concentration of ( FSO2 ) 2NLi in electrolytic solution DEC : diethyl carbonate L was 3.9 mol/ L , and the density of electrolytic solution L ( Nonaqueous Electrolyte Secondary Battery ) was 1.44 g / cm . In the following, the nonaqueous electrolyte secondary ( Electrolytic Solution M ) 50 batteries ( 1 ) to ( 5 ) are described specifically. Since the With a method similar to that of electrolytic solution L , following Examples are described in separate sections for electrolytic solution M whose concentration of ( FSO2 ) 2NLi convenience sake , duplications may exist . In some cases , the was 2.9 mol / L and whose density was 1.36 g /cm was following Examples, and EB and CB described later corre produced. spond to the multiple Examples of the nonaqueous electro ( Electrolytic Solution N ) 55 lyte secondary batteries ( 1 ) to ( 5 ) . Approximately 5 mL of ethyl methyl carbonate, which is < Nonaqueous Electrolyte Secondary Battery ( 1 ) > an organic solvent, was placed in a flask including a stirring bar . Under a stirring condition , with respect to ethyl methyl Example 1-1 carbonate in the flask , ( FSO2 ) 2NLi , which is a lithium salt , was gradually added to be dissolved . A total amount of 12.81 60 A nonaqueous electrolyte secondary battery of Example g of ( FSO2 ) 2NLi was added to the flask , and stirring was 1-1 was produced using electrolytic solution E8 . performed overnight in the flask . The obtained electrolytic < Negative Electrode > solution was transferred to a 20 - ml measuring flask , and A SNO grade ( mean particle diameter of 15 um ) graphite ethyl methyl carbonate was added thereto until a volume of (hereinafter , sometimes referred to as graphite ( A ) ) from 20 mL was obtained . This was used as electrolytic solution 65 SEC CARBON , Ltd., and polyvinylidene fluoride ( PVDF ) N. The production was performed within a glovebox under were added to , and mixed with N -methyl - 2 -pyrrolidone an inert gas atmosphere . (NMP ) to prepare a negative electrode mixture in a slurry US 11,011,781 B2 51 52 form . The composition ratio of each component ( solid ite ( C ) similarly to Example 1-1 , the G / D ratio , which is a content) in the slurry was graphite :PVdF = 90 : 10 ( mass ratio of intensities of G - band and D - band peaks, was 16.0 . ratio ). Raman spectrum analysis was performed on a powder of Example 1-4 the graphite ( A ). As a device , RAMAN - 11 ( excitation wave 5 length 9 = 532 nm , grating: 600 gr /mm , laser power : 0.02 A nonaqueous electrolyte secondary battery of Example mW ) manufactured by Nanophoton Corporation was used . 1-4 was obtained similarly to Example 1-3 except for using In the Raman spectrum , a G / D ratio , which is a ratio of electrolytic solution E11 . intensities of G -band and D - band peaks , was 12.2 . The slurry was applied on the surface of an electrolytic 10 Comparative Example 1-1 copper foil ( current collector ) having a thickness of 20 um using a doctor blade to form a negative electrode active A negative electrode was produced similarly to that of material layer on the copper foil . Example 1-1 except for using, instead of graphite ( A ), a Then , the organic solvent was removed from the negative graphite with a product name SG - BH ( mean particle diam electrode active material layer through volatilization by 15 eter of 20 um ) ( hereinafter, sometimes referred to as graphite drying the negative electrode active material layer at 80 ° C. ( D ) ) from Ito Graphite Co. , Ltd. Otherwise, a nonaqueous for 20 minutes. After the drying, the current collector and the electrolyte secondary battery of Comparative Example 1-1 negative electrode active material layer were attached firmly and joined by using a roll press machine . The obtained was obtained similarly to Example 1-1 . When Raman spec joined object was vacuum dried at 120 ° C. for 6 hours to 20 trum analysis was performed on the used graphite ( D ) form a negative electrode whose thickness of the negative similarly to Example 1-1 , the G / D ratio , which is a ratio of electrode active material layer was about 30 um . intensities of G -band and D - band peaks , was 3.4 . In the negative electrode, the negative electrode active Comparative Example 1-2 material layer had a weight per area of 2.3 mg/ cm² and a density of 0.86 g /cm 25 A negative electrode was produced similarly to that of < Nonaqueous Electrolyte Secondary Battery > Example 1-1 except for using, instead of graphite ( A ), a By using the produced negative electrode as an evaluation graphite with a product name SG - BH8 (mean particle diam electrode, a nonaqueous electrolyte secondary battery was eter 8 um ) (hereinafter , sometimes referred to as graphite produced. A metallic lithium foil ( thickness of 500 um ) was ( E ) ) from Ito Graphite Co. , Ltd. Otherwise, a nonaqueous used as a counter electrode . This nonaqueous electrolyte 30 electrolyte secondary battery of Comparative Example 1-2 secondary battery is a nonaqueous electrolyte secondary was obtained similarly to Example 1-1 . When Raman spec battery for evaluation, i.e. , a half - cell . trum analysis was performed on the used graphite ( E ) The counter electrode and the evaluation electrode were similarly to Example 1-1 , the G / D ratio , which is a ratio of respectively cut to have diameters of 13 mm and 11 mm , and intensities of G - band and D -band peaks , was 3.2 . a separator (Whatman glass fiber filter paper ) having a 35 thickness of 400 um was interposed therebetween to form an Comparative Example 1-3 electrode assembly battery . This electrode assembly battery was housed in a battery case ( CR2032 coin cell manufac- A nonaqueous electrolyte secondary battery of Compara tured by Hohsen Corp. ). Electrolytic solution E8 was tive Example 1-3 was obtained similarly to Example 1-1 injected therein , and the battery case was sealed to obtain a 40 except for using electrolytic solution C5 instead of the nonaqueous electrolyte secondary battery of Example 1-1 . electrolytic solution of the present invention . Details of the lithium battery of Example 1-1 and nonaque ous electrolyte secondary batteries of the following Comparative Example 1-4 Examples and Comparative Examples are shown in Table 41 provided at the end of the section of the Examples . 45 A nonaqueous electrolyte secondary battery of Compara tive Example 1-4 was obtained similarly to Example 1-2 Example 1-2 except for using electrolytic solution C5 instead of the electrolytic solution of the present invention . A negative electrode was produced similarly to that of Example 1-1 except for using , instead of graphite ( A ), an 50 Comparative Example 1-5 SNO grade ( mean particle diameter of 10 um ) graphite ( hereinafter, sometimes referred to as graphite ( B ) ) from A nonaqueous electrolyte secondary battery of Compara SEC CARBON , Ltd. Otherwise, a nonaqueous electrolyte tive Example 1-5 was obtained similarly to Example 1-3 secondary battery of Example 1-2 was obtained similarly to except for using electrolytic solution C5 instead of the Example 1-1 . When Raman spectrum analysis was per- 55 electrolytic solution of the present invention . formed on the used graphite ( B ) similarly to Example 1-1 , the G / D ratio , which is a ratio of intensities of G -band and Comparative Example 1-6 D - band peaks , was 4.4 . A nonaqueous electrolyte secondary battery of Compara Example 1-3 60 tive Example 1-6 was obtained similarly to Comparative Example 1-1 except for using electrolytic solution C5 A negative electrode was produced similarly to that of instead of the electrolytic solution of the present invention . Example 1-1 except for using, instead of graphite ( A ) , graphite ( C ) having a mean particle diameter of 10 um . Comparative Example 1-7 Otherwise , a nonaqueous electrolyte secondary battery of 65 Example 1-3 was obtained similarly to Example 1-1 . When A nonaqueous electrolyte secondary battery of Compara Raman spectrum analysis was performed on the used graph- tive Example 1-7 was obtained similarly to Comparative US 11,011,781 B2 53 54 Example 1-2 except for using electrolytic solution C5 < Nonaqueous Electrolyte Secondary Battery > instead of the electrolytic solution of the present invention . By using the positive electrode, the negative electrode, The configuration of the nonaqueous electrolyte second and electrolytic solution E8 described above , a laminated type lithium ion secondary battery, which is one type of the ary batteries of Examples 1-1 to 1-4 and Comparative 5 nonaqueous electrolyte secondary battery, was produced. In Examples 1-1 to 1-7 are shown in Table 6 . detail, a 260 - um thick filter paper for experiments was interposed between the positive electrode and the negative TABLE 10 electrode as a separator to form an electrode assembly. The Graphite Graphite electrode assembly was covered with a set of two sheets of Electrolytic solution type G / D ratio a laminate film . The laminate film was formed into a 10 bag - like shape by having three sides thereof sealed , and the Example 1-1 E8 ( 4.5M LiFSA / AN ) Graphite ( A ) 12.2 Example 1-2 E8 ( 4.5M LiFSA / AN ) Graphite ( B ) 4.4 electrolytic solution of the present invention was injected Example 1-3 E8 ( 4.5M LiFSA / AN ) Graphite ( C ) 16.0 therein . Four sides were sealed airtight by sealing the Example 1-4 E11 ( 3.9M L?FSA / DMC ) Graphite ( C ) 16.0 remaining one side to obtain a laminated type lithium ion Comparative E8 ( 4.5M LiFSA / AN ) Graphite ( D ) 3.4 secondary battery in which the electrode assembly and the Example 1-1 15 electrolytic solution were sealed . The positive electrode and Comparative E8 ( 4.5M LiFSA / AN ) Graphite ( E ) 3.2 Example 1-2 the negative electrode each include a tab enabling electrical Comparative C5 ( 1M LIPF / EC + DEC ( 3 : 7 ) ) Graphite ( A ) 12.2 connection to the outside , and one part of the tab extends Example 1-3 outside the laminated type lithium ion secondary battery. Comparative C5 ( 1M LIPF / EC + DEC ( 3.7 ) ) Graphite ( B ) 4.4 Example 1-4 20 Example 1-6 Comparative C5 ( 1M LIPF /EC + DEC ( 3 : 7 ) ) Graphite ( C ) 16.0 Example 1-5 Comparative C5 ( 1M LiPF /EC + DEC ( 3.7 ) ) Graphite ( D ) 3.4 A nonaqueous electrolyte secondary battery of Example Example 1-6 1-6 was produced similarly to Example 1-5 except for using Comparative C5 ( 1M LiPF / EC + DEC ( 3 : 7 ) ) Graphite ( E ) 3.2 electrolytic solution E4 . Example 1-7 25 Comparative Example 1-8 Evaluation Example 9 : Cyclic Voltammetry A nonaqueous electrolyte secondary battery of Compara tive Example 1-8 was obtained similarly to Example 1-5 With respect to the nonaqueous electrolyte secondary 30 except for using electrolytic solution C5 instead of the battery of Examples 1-1 to 1-4 and Comparative Examples electrolytic solution of the present invention . 1-1 to 1-7 , cyclic voltammetry ( i.e. , CV ) measurement was performed with a condition of temperature: 25 ° C. , sweep Evaluation Example 10 : Thermal Stability rate : 0.1 mV / sec , voltage range: 0.01 V to 2 V , and 1 to 5 35 Each of the nonaqueous electrolyte secondary batteries of cycles . The results are shown in FIGS . 36 to 45. In the Examples 1-5 and 1-6 and Comparative Example 1-8 was nonaqueous electrolyte secondary batteries of Examples 1-1 fully charged under constant current constant voltage con to 1-4 , a reversible redox reaction was confirmed similarly ditions to obtain an electric potential difference of 4.2 V. The to the nonaqueous electrolyte secondary batteries of Com nonaqueous electrolyte secondary battery was disassembled parative Examples 1-1 to 1-7 ( i.e. , conventional nonaqueous 40 after being fully charged , and the negative electrode thereof electrolyte secondary batteries ). As in the nonaqueous elec was removed . 2.8 mg of the negative electrode and 1.68 UL trolyte secondary batteries of Comparative Examples 1-1 of an electrolytic solution were placed in a stainless steel and 1-2 , reversible redox reaction was confirmed even pan , and the pan was sealed . Differential scanning calorim when a graphite whose G / D ratio was lower than 3.5 was etry analysis was performed using the sealed pan under a used . Thus, the electrolytic solution of the present invention 45 nitrogen atmosphere at a temperature increase rate of 20 ° is recognized to be usable for a nonaqueous electrolyte C./min . , and a DSC curve was observed . FIGS . 46 and 47 secondary battery when a graphite is used as the negative respectively show a DSC chart of the nonaqueous electrolyte electrode active material, regardless of the G / D ratio . secondary batteries of Example 1-5 and Comparative Example 1-8 and a DSC chart of the nonaqueous electrolyte Example 1-5 50 secondary batteries of Example 1-6 and Comparative Example 1-8 . In a nonaqueous electrolyte secondary battery of Example In a fully charged nonaqueous electrolyte secondary bat 1-5 , the same negative electrode as in Example 1-1 was tery using a graphite as the negative electrode active mate used . rial, when a general electrolytic solution was used and heat < Positive Electrode > 55 was applied , multiple exothermic reactions occur at 300 ° C. As the positive electrode active material, Li or lower as in Comparative Example 1-8 . However, since the [ Nio.sCoo2Mn..3 ] 02 , acetylene black ( AB ) , and PVdF were exothermic peaks that appeared at positions shown with added to , and mixed with NMP to prepare a positive arrows in the figures disappeared , the reactivity between the electrode mixture in a slurry form . The composition ratio of graphite negative electrode and the electrolytic solution of each component ( solid content) in the slurry is active 60 the present invention was low , revealing excellent thermo material :AB :PVdF = 94 : 3 : 3 ( mass ratio ). The slurry was physical property in Examples 1-5 and 1-6 using the elec applied on the surface of an aluminum foil ( current collec- trolytic solution of the present invention . tor ) using a doctor blade , and dried to produce a positive electrode having a positive electrode active material layer Evaluation Example 11 : Rate Characteristics with a thickness of approximately 25 um . Hereinafter, if 65 necessary , Li [Nio5C002Mn 3 ]02 is referred to as By using the nonaqueous electrolyte secondary batteries NCM523 . of Example 1-1 and Comparative Example 1-1 , respective US 11,011,781 B2 55 56 rate capacity characteristics were evaluated under the fol- electrolytic solution of the present invention and the nega lowing conditions . The results are shown in FIG . 48 . tive electrode whose negative electrode active material is a ( 1 ) Current is supplied in a direction that causes occlusion graphite having a G / D ratio of not lower than 3.5 . Further of lithium to the negative electrode . more , based on comparison of Examples, since rate capacity ( 2 ) Voltage range: From 2 V down to 0.01 V ( v.s. Li / Li * ) 5 characteristics and cycle capacity retention rates tend to ( 3 ) Rate : 0.1C , 0.2C , 0.5C , 1C , 2C , 5C , 10C , and 0.1C improve more when the G / D ratio is higher, the G / D ratio is ( stop current after reaching 0.01 V ) . thought to be more preferably not lower than 10. From this ( 4 ) Three measurements at each rate ( a total of 24 cycles ) . result, an electrolytic solution was revealed to also be the Here , “ 1C ” represents a current value required for fully electrolytic solution of the present invention even when both chargingcurrent . or discharging a battery in 1 hour under constant 10 AN was used and when DMC was used as the organic The nonaqueous electrolyte secondary battery of Example solvent for the electrolytic solution , and rate capacity char 1-1 displayed a current capacity approximately twice of that acteristics and cycle capacity retention rate were revealed to in Comparative Example 1-1 in a range from 0.5C to 2C , and improve when the graphite whose G / D ratio is not lower revealed to be capable of high - speed charging. 15 than 3.5 was used in combination . Evaluation Example 12 : Rate Characteristics , Cycle Example 1-7 Durability < Negative Electrode > By using the nonaqueous electrolyte secondary batteries 20 A SNO grade (mean particle diameter 15 um ) graphite of Examples 1-1 to 1-3 and Comparative Examples 1-1 to ( hereinafter, sometimes referred to as graphite ( A ) ) from 1-3 and 1-7 , rate capacity characteristics and cycle capacity SEC CARBON , Ltd. , was used as the negative electrode retention rates were evaluated . active material. 98 parts by mass of graphite ( A ), which is ( 1 ) Current is supplied in a direction that causes occlusion a negative electrode active material, 1 part by mass of a of lithium to the negative electrode. 25 styrene butadiene rubber, which is a binding agent, and 1 ( 2 ) Voltage range; 0.01 V to 2 V ( vs. Li ) part by mass of carboxymethyl cellulose were mixed . The ( 3 ) Rate : 0.1C , 0.2C , 0.5C , 1C , 2C , 5C , 10C , and 0.1C mixture was dispersed in a proper amount of ion exchanged ( stop current after reaching 0.01 V ) . water to prepare a negative electrode mixture in a slurry ( 4 ) Three measurements at each rate ( a total of 24 cycles ) . form . Hereinafter, if necessary , the styrene butadiene rubber ( 5 ) Temperature : Room temperature . 30 is abbreviated as SBR , and carboxymethyl cellulose is Current capacities at 0.1C rate and 2C rate were measured abbreviated as CMC . using the above described conditions , and a ratio of a current Raman spectrum analysis was performed on a powder of capacity at 2C rate with resp to a current capacity at 0.1C the graphite ( A ). As a device , RAMAN - 11 ( excitation wave rate was used as rate capacity characteristics . In addition , length ? = 532 nm , grating: 1800 gr/ mm , laser power : mW ) charging and discharging were repeated for 25 cycles at 35 manufactured by Nanophoton Corporation was used . In the 0.2C , and a ratio of a current capacity at the 25 - th cycle with Raman spectrum , a G / D ratio , which is a ratio of intensities respect to a current capacity at the first cycle was used as a of G -band and D -band peaks, was 12.2 . cycle capacity retention rate . The results are shown in Table The slurry was applied on the surface of an electrolytic 11 . copper foil ( current collector) having a thickness of 20 um TABLE 11 Rate capacity Cycle capacity Electrolytic Graphite characteristic retention rate 25 cyc / solution G / D ratio 2 C / 0.1 C 1 cyc Example 1-1 E8 ( 4.5M LiFSA / AN ) 12.2 0.53 0.98 Example 1-2 E8 ( 4.5M LiFSA / AN ) 4.4 0.46 0.92 Example 1-3 E8 ( 4.5M LiFSAAN ) 16.0 0.60 0.99 Example 1-4 E11 ( 3.9M LiFSA / DMC ) 16.0 0.50 0.97 Comparative E8 ( 4.5M LiFSA / AN ) 3.4 0.30 0.70 Example 1-1 Comparative E8 ( 4.5M LiFSA / AN ) 3.2 0.35 0.62 Example 1-2 Comparative C5 ( 1M 12.2 0.15 0.99 Example 1-3 LiPF / EC + DEC ( 3 : 7 ) ) Comparative C5 ( 1M 3.2 0.23 0.98 Example 1-7 LIPFLEC + DEC ( 3 : 7 ) )

As seen in Comparative Examples 1-1 and 1-2 , cycle using a doctor blade to form a negative electrode active capacity retention rates cannot be easily improved by simply material layer on the copper foil. combining the electrolytic solution of the present invention Then , the organic solvent was removed from the negative and the negative electrode whose negative electrode active 60 material is a graphite having a G / D ratio lower than 4. In electrode active material layer through volatilization by addition , as seen in Comparative Examples 1-3 and 1-7 , drying the negative electrode active material layer at 80 ° C. when a conventional electrolytic solution was used , rate for 20 minutes . After the drying, the current collector and the lesscapacity of the characteristics G /D ratio of cannot the graphite be easily . However improved, as regardseen in 65 negative electrode active material layer were attached firmly Examples 1-1 to 1-3 , rate capacity characteristics and cycle and joined by using a roll press machine. The obtained capacity retention rates are both improved by combining the joined object was vacuum dried at 100 ° C. for 6 hours to US 11,011,781 B2 57 58 form a negative electrode whose weight per area of the seconds after the start of charging , and “ 5 - second input " negative electrode active material layer was about 8.5 refers to an input inputted at 5 seconds after the start of mg/ cm ? charging . < Positive Electrode > In Tables 12 and 13 , the electrolytic solution of the present A positive electrode includes a positive electrode active 5 invention used in Example 1-7 is abbreviated as “ FSA , ” and material layer, and a current collector coated with the the electrolytic solution used in Comparative Example 1-9 is positive electrode active material layer . The positive elec- abbreviated as “ ECPF .” trode active material layer includes a positive electrode active material, a binding agent, and a conductive additive . TABLE 12 The positive electrode active material is formed of 10 LiNiosCoo2Mn0.302. The binding agent is formed of PVDF Example Comparative Example 1-9 and the conductive additive is formed of AB . The current Graphite 1-7 Graphite ( A ) Graphite ( A ) collector is formed from an aluminum foil having a thick- Electrolytic solution FSA ECPF ness of 20 um . The contained mass ratio of the positive 2 -second input (mW ) 958.3 817.2 1255.0 797.3 electrode active material , the binding agent, and the con- 15 1127.5 785.3 ductive additive is 94 : 3 : 3 when mass of the positive elec 5 - second input ( mW ) 737.1 617.1 trode active material layer is defined as 100 parts by mass . 973.5 602.8 In order to produce the positive electrode , NCM523 , 864.0 585.0 PVDF , and AB were mixed in the above described mass ratio , and NMP was added thereto as the solvent to obtain a 20 positive electrode material in a paste form . The positive ( 25 ° C. , SOC80 % ) electrode material in the paste form was applied on the surface of the current collector using a doctor blade to form TABLE 13 the positive electrode active material layer. The positive Example 1-7 Comparative Example 1-9 electrode active material layer was dried for 20 minutes at 25 Graphite Graphite ( A ) Graphite ( A ) 80 ° C. to remove the NMP through volatilization . An Electrolytic solution FSA ECPF aluminum foil having the positive electrode active material 2 - second input ( mW ) 362.9 189.2 layer formed on the surface thereof was compressed using a 482.6 204.4 roll press machine to firmly attach and join the aluminum 424.0 195.7 30 5 - second input (mW ) 298.7 163.3 foil and the positive electrode active material layer. The 396.4 199.1 obtained joined object was heated in a vacuum dryer for 6 350.7 191.3 hours at 120 ° C. and cut in a predetermined shape to obtain the positive electrode . < Nonaqueous Electrolyte Secondary Battery > ( 0 ° C. , SOC80 % ) A nonaqueous electrolyte secondary battery of Example 35 At both 0 ° C. and 25 ° C. , Example 1-7 displayed improve 1-7 was obtained similarly to Example 1-5 except for using ment in input ( charging) characteristics when compared to the positive electrode , the negative electrode , and electro Comparative Example 1-9 . This is the effect of using the lytic solution E8 described above , and cellulose nonwoven electrolytic solution of the present invention and the graphite fabric ( thickness of 20 um ) as the separator. whose GD ratio is not lower than 3.5 , and , since high input 40 ( charging) characteristics were shown particularly even at 0 ° Comparative Example 1-9 C. , movement of lithium ions in the electrolytic solution is shown to occur smoothly even at a low temperature . A nonaqueous electrolyte secondary battery of Compara tive Example 1-9 was obtained similarly to Example 1-7 Example 1-8 except for using electrolytic solution C5 instead of the 45 electrolytic solution of the present invention . A nonaqueous electrolyte secondary battery of Example 1-8 using electrolytic solution E11 was produced in the Evaluation Example 13 : Input Characteristics following manner. < Negative Electrode > By using the lithium ion batteries of Example 1-7 and 50 90 parts by mass of a natural graphite having a mean Comparative Example 1-9 , input ( charging ) characteristics particle diameter 10 um , which is an active material, and 10 were evaluated using the following conditions. parts by mass of PVDF , which is a binding agent, were ( 1 ) Usage voltage range: 3 V to 4.2 V mixed . The mixture was dispersed in a proper amount of ( 2 ) Capacity: 13.5 mAh NMP to create a slurry. As the current collector, a copper foil ( 3 ) SOC : 80 % 55 having a thickness of 20 um was prepared . 2.46 mg of the ( 4 ) Temperature: 0 ° C. , 25 ° C. slurry was applied in a film form on the surface of the copper ( 5 ) Number of measurements : Three times each foil by using a doctor blade . The natural graphite used in The used evaluation conditions were : state of charge Example 1-8 had a G / D ratio of 4.4 . ( SOC ) of 80 % , 0 ° C. or 25 ° C. , usage voltage range of 3 V The copper foil on which the slurry was applied was dried to 4.2 V , and capacity of 13.5 mAh . SOC 80 % at 0 ° C. is in 60 to remove NMP, and then the copper foil was pressed to a range in which input characteristics are unlikely to be obtain a joined object. The obtained joined object was exerted such as , for example , when used in a cold room . heated and dried in a vacuum dryer for 6 hours at 120 ° C. Evaluation of input characteristics of Example 1-7 and to obtain a copper foil having the active material layer Comparative Example 1-9 was performed three times each formed thereon . This was used as the working electrode. The for 2 - second input and 5 - second input. Evaluation results of 65 mass of the active material on the copper foil was 2.214 mg . input characteristics are shown in Tables 12 and 13. In the The mass of the active material per 1 cm2 of the copper foil tables , “ 2 - second input ” refers to an input inputted at 2 was 1.48 mg . Furthermore, the density of the natural graph US 11,011,781 B2 59 60 ite and the PVdF before being pressed was 0.68 g / cm " , and batteries, at 0.1C , 0.2C , 0.5C , 1C , and 2C rates , charging and the density of the active material layer after being pressed then discharging were performed , and the discharge capacity was 1.025 g /cm . of the working electrode was measured at each rate . “ 1C ” < Nonaqueous Electrolyte Secondary Battery > refers to a current required for fully charging or discharging Metal Li was used as the counter electrode . 5 a battery in 1 hour under a constant current. In the descrip The working electrode, the counter electrode , and elec tion here, the counter electrode was regarded as the negative trolytic solution E11 were housed in a battery case ( CR2032 electrode and the working electrode was regarded as the type coin cell case manufactured by Hohsen Corp.) having positive electrode. With respect to the capacity of the a diameter of 13.82 mm to obtain a nonaqueous electrolyte working electrode at 0.1C rate , proportions of capacities at 10 other rates, i.e. , rate characteristics, were calculated . The secondary battery of Example 1-8 . results are shown in Table 15 . Example 1-9 TABLE 15 A nonaqueous electrolyte secondary battery of Example Exam Exam- Comparative 1-9 was obtained with a method similar to that of Example 15 Example ple Example ple Example 1-8 except for using electrolytic solution E8 instead of 1-8 1-9 1-10 1-11 1-10 electrolytic solution E11 . 0.2 C capacity 0.982 0.981 0.981 0.985 0.974 0.1 C capacity Example 1-10 0.5 C capacity 0.961 0.955 0.956 0.960 0.931 20 0.1 C capacity 1 C capacity 0.925 0.915 0.894 0.905 0.848 A nonaqueous electrolyte secondary battery of Example 0.1 C capacity 1-10 was obtained with a method similar to that of Example 2 C capacity 0.840 0.777 0.502 0.538 0.575 1-8 except for using electrolytic solution E16 instead of 0.1 C capacity electrolytic solution E11 . 25 In the nonaqueous electrolyte secondary batteries of Example 1-11 Examples 1-8 to 1-11 , at 0.2C , 0.5C , and 1C rates , decrease in capacity was suppressed compared to in the nonaqueous A nonaqueous electrolyte secondary battery of Example electrolyte secondary battery of Comparative Example 1-10 . 1-11 was obtained with a method similar to that of Example Based on this result, the nonaqueous electrolyte secondary 1-8 except for using electrolytic solution E19 instead of 30 battery of each of the Examples, i.e. , the nonaqueous elec electrolytic solution E11 . trolyte secondary battery of the present invention , was confirmed to show excellent rate characteristics . Further Comparative Example 1-10 more , in the nonaqueous electrolyte secondary batteries of Examples 1-8 and 1-9 , at 2C rate , decrease in capacity was A nonaqueous electrolyte secondary battery of Compara- 35 suppressed compared to in the nonaqueous electrolyte sec tive Example 1-10 was obtained similarly to Example 1-8 ondary battery of Comparative Example 1-10 . Thus, the except for using electrolytic solution C5 instead of electro nonaqueous electrolyte secondary batteries of Examples 1-8 lytic solution E11 . and 1-9 display particularly excellent rate characteristics. Evaluation Example 14 : Reversibility of Reaction 40 Evaluation Example 16 : Capacity Retention Rate With respect to each of the nonaqueous electrolyte sec ondary batteries of Examples 1-8 to 1-11 and Comparative Capacity retention rates of the nonaqueous electrolyte Example 1-10 , a charging /discharging test was performed secondary battery of Examples 1-8 to 1-11 and Comparative for three times using the conditions shown in Table 14. 45 Example 1-10 were tested using the following method . Respective charging/ discharging curves obtained therefrom With respect to each of the nonaqueous electrolyte sec are shown in FIGS . 49 to 53 . ondary batteries, a charging /discharging cycle from 2.0 V to Similarly to a general nonaqueous electrolyte secondary 0.01 V , which is CC charging ( constant current charging ) to battery of Comparative Example 1-10 , the nonaqueous a voltage of 2.0 V and CC discharging ( constant current electrolyte secondary batteries of Examples 1-8 to 1-11 are 50 Indischarging detail, firstly) to ,a chargingvoltage of and 0.01 discharging V , was performed were performed at 25 ° C. understood as to undergo charging / discharging reactions for three cycles at a charging / discharging rate of 0.1C . Then , reversibly . charging and discharging were performed for three cycles at respective charging / discharging rates of 0.2C , 0.5C , 1C , 2C , TABLE 14 5C , and 10C , sequentially. Lastly , charging and discharging 55 Cut -off voltage Current rate were performed for three cycles at 0.1C . Capacity retention rate ( % ) of each of the nonaqueous electrolyte secondary CC charging 0.01 V 0.1 C CC discharging 2.0 V 0.1 C batteries was obtained from the following formula . Capacity Retention rate ( % ) = B / Ax100 Temperature: 25 ° C. , Cycle number : 3 60 A : Second discharge capacity of the working electrode in the first charging / discharging cycle at 0.1C Evaluation Example 15 : Rate Characteristics B : Second discharge capacity of the working electrode in the last charging / discharging cycle at 0.1C Rate characteristics of the nonaqueous electrolyte second- The results are shown in Table 16. In the description here , ary battery of Examples 1-8 to 1-11 and Comparative 65 the counter electrode was regarded as the negative electrode Example 1-10 were tested using the following method . With and the working electrode was regarded as the positive respect to each of the nonaqueous electrolyte secondary electrode . US 11,011,781 B2 61 62 TABLE 16 TABLE 17 - continued Comparative Example 1-2 Comparative Example 1-4 Example Example Example Example Example 1-8 1-9 1-10 1-11 1-10 1 C capacity / 0.1 C capacity 0.868 0.498 5 2 C capacity / 0.1 C capacity 0.471 0.177 Capacity 98.1 98.7 98.9 99.8 98.8 retention rate When compared to the nonaqueous electrolyte secondary ( % ) battery of Comparative Example 1-4 , the nonaqueous elec trolyte secondary battery of Example 1-2 showed suppres 10 sion of decrease in capacity at all rates of 0.2C , 0.5C , 1C , All the nonaqueous electrolyte secondary batteries per and 2C . Thus , the nonaqueous electrolyte secondary battery formed the charging / discharging reaction finely, and dis of Example 1-2 displayed excellent rate characteristics. Also played suitable capacity retention rate . In particular, capac based on this ult , the nonaqueous electrolyte secondary ity retention rates of the half - cells of Example 1-9 , 1-10 , and battery of the present invention using the electrolytic solu 1-11 were significantly superior. 15 tion of the present invention was confirmed to show excel Example 1-12 lent rate characteristics . Evaluation Example 19 : Responsivity with Respect A nonaqueous electrolyte secondary battery of Example to Repeated Rapid Charging /Discharging 1-12 was obtained similarly to Example 1-2 except for using 20 electrolytic solution E9 . The changes in capacity and voltage were observed when charging and discharging were repeated three times at 1C Evaluation Example 17 : Rate Characteristics at rate using the nonaqueous electrolyte secondary batteries of Low Temperature Example 1-2 and Comparative Example 1-4 . The results are 25 shown in FIG . 56 . By using the nonaqueous electrolyte secondary batteries Associated with repeated charging and discharging, the of Example 1-12 and Comparative Example 1-4 , rate char- nonaqueous electrolyte secondary battery of Comparative acteristics at -20 ° C. were evaluated in the following Example 1-4 tended to show greater polarization when manner . The results are shown in FIGS . 54 and 55 . current was passed therethrough at 1C rate , and capacity ( 1 ) Current is supplied in a direction that causes occlusion 30 obtained from 2 V to 0.01 V rapidly decreased . On the other of lithium to the negative electrode ( evaluation electrode ). hand, the nonaqueous electrolyte secondary battery of ( 2 ) Voltage range : From 2 V down to 0.01 V ( v.s. Li / Li * ) . Example 1-2 hardly displayed increase or decrease of polar ( 3 ) Rate : 0.02C , 0.05C , 0.1C , 0.2C , and 0.5C ( stop current ization even when charging and discharging were repeated , after reaching 0.01 V ) . and had maintained its capacity suitably . This is confirmed “ 10 ” represents a current value required for fully charg- 35 from the manner three curves overlap in FIG . 56 . ing or discharging a battery in 1 hour under constant current . A conceivable reason why polarization increased in the Based on FIGS . 54 and 55 , voltage curves of the non- nonaqueous electrolyte secondary battery of Comparative aqueous electrolyte secondary battery of Example 1-12 at Example 1-4 is the inability of the electrolytic solution to each current rate are understood as to display high voltage supply sufficient amount of Li to a reaction interface with an compared to the voltage curves of the nonaqueous electro- 40 electrode because of Li concentration unevenness generated lyte secondary battery of Comparative Example 1-4 . Based in the electrolytic solution when charging and discharging on this result , the nonaqueous electrolyte secondary battery are repeated rapidly, i.e. , uneven distribution of Li concen of the present invention was confirmed to show excellent tration in the electrolytic solution . In the nonaqueous elec trolyte secondary battery of Example 1-2 , using the electro rate characteristics even in a low -temperature environment. 45 lytic solution of the present invention having a high Li Evaluation Example 18 : Rate Characteristics concentration is thought to have enabled suppression of uneven distribution of Li concentration of the electrolytic Rate characteristics of the nonaqueous electrolyte second solution . Also based on this result , the nonaqueous electro ary batteries of Example 1-2 and Comparative Example 1-4 lyte secondary battery of the present invention using the were tested using the following method . 50 electrolytic solution of the present invention was confirmed With respect to each of the nonaqueous electrolyte sec- to show excellent responsivity against rapid charging /dis ondary batteries, at 0.1C , 0.2C , 0.5C , 1C , and 2C rates, charging charging and then discharging were performed , and the < Nonaqueous Electrolyte Secondary Battery ( 2 ) > capacity (discharge capacity ) of the working electrode was measured at each rate . Here, the counter electrode was 55 Example 2-1 regarded as the negative electrode and the working electrode was regarded as the positive electrode, and rate character- < Negative Electrode > istics were calculated similarly to that described above . The A hard carbon whose crystallite size ( L ) was 1.1 nm and polyvinylidene fluoride ( PVDF ) were added to , and mixed in results are shown in Table 17 . 60 N -methyl - 2 - pyrrolidone (NMP ) to prepare a negative elec trode mixture in a slurry form . The composition ratio of each TABLE 17 component ( solid content) in the slurry was hard carbon : Example 1-2 Comparative Example 1-4 PVdF = 9 : 1 ( mass ratio ). 0.1 C capacity (mAh / g ) 334 330 Measurement of the crystallite size was performed with 0.2 C capacity /0.1 C capacity 0.983 0.966 65 an X -ray diffraction method using Cu K - a radiation as an 0.5 C capacity /0.1 C capacity 0.946 0.767 X - ray source , and the crystallite size was calculated using the Scherrer's equation based on a halfwidth of a diffraction US 11,011,781 B2 63 64 peak detected at a diffraction angle 20 = 20 degrees to 30 as to have excellent rate capacity characteristics over the degrees and the diffraction angle . [ SmartLab ] manufactured nonaqueous electrolyte secondary battery of Comparative by Rigaku Corporation was used as the measuring device , Example 2-1 , and functions as a battery appropriate for and focusing method was used for the optical system . high -speed charging and high input -output . The slurry was applied on the surface of an electrolytic 5 copper foil ( current collector ) having a thickness of 20 um Example 2-2 using a doctor blade to form a negative electrode active A negative electrode was produced similarly to that of material layer on the copper foil. Example 1-1 except for choosing a soft carbon whose electrodeThen , the active organic material solvent layer was throughremoved fromvolatilization the negative by 10 crystallite size ( L ) was 4.2 nm and using this soft carbon. drying the negative electrode active material layer at 80 ° C. Other than using this negative electrode, a nonaqueous for 20 minutes . After the drying, the current collector and the electrolyte secondary battery of Example 2-2 was obtained negative electrode active material layer were attached firmly similarly to Example 1-1 . and joined by using a roll press machine . The obtained joined object was heated and dried under vacuum at 120 ° C. 15 Example 2-3 for 6 hours to form a negative electrode whose thickness of A nonaqueous electrolyte secondary battery of Example the negative electrode active material layer was about 30 2-3 was obtained similarly to Example 2-1 except for using um <. Nonaqueous Electrolyte Secondary Battery > electrolytic solution E11 . By using the produced negative electrode described above 20 Example 2-4 as an evaluation electrode , a nonaqueous electrolyte second ary battery was produced . A metallic lithium foil ( thickness A nonaqueous electrolyte secondary battery of Example of 500 um ) was used as a counter electrode . 2-4 was obtained similarly to Example 2-2 except for using The counter electrode and the evaluation electrode were respectively cut to have diameters of 13 mm and 11 mm , and 25 the same electrolytic solution E11 as in Example 2-3 . a separator (Whatman glass fiber filter paper) having a Comparative Example 2-2 thickness of 400 um was interposed therebetween to form an electrode assembly battery . This electrode assembly battery A negative electrode was produced similarly to Example was housed in a battery case ( CR2032 coin cell manufac 2-1 except for selecting and using a graphite whose crys tured by Hohsen Corp.) . Electrolytic solution E8 was 30 tallite size ( L ) was 28 nm . A nonaqueous electrolyte sec injected therein , and the battery case was sealed to obtain a ondary battery of Comparative Example 2-2 was obtained nonaqueous electrolyte secondary battery of Example 2-1 . similarly to that of Example 2-1 except for using this Details of the nonaqueous electrolyte secondary battery of Example 2-1 and nonaqueous electrolyte secondary batteries negative electrode. of the following Examples and Comparative Examples are 35 Comparative Example 2-3 shown in Table 42 provided at the end of the section of the Examples A negative electrode was produced similarly to Example 2-1 except for selecting and using a graphite whose crys Comparative Example 2-1 tallite size ( L ) was 42 nm . A nonaqueous electrolyte sec 40 ondary battery of Comparative Example 2-3 was obtained A nonaqueous electrolyte secondary battery of Compara similarly to that of Example 2-1 except for using this tive Example 2-1 was obtained similarly to Example 2-1 negative electrode . except for using electrolytic solution C5 instead of electro lytic solution E8 . Comparative Example 2-4 45 Evaluation Example 20 : Reversibility of Charging A negative electrode was produced similarly to Example and Discharging 2-1 using a similar hard carbon as in Example 2-1 . A nonaqueous electrolyte secondary battery of Comparative Respective rate capacity characteristics of the nonaqueous Example 2-4 was obtained similarly to that of Example 2-1 electrolyte secondary batteries of Example 2-1 and Com- 50 except for using this negative electrode and using electro parative Example 2-1 were evaluated under the following lytic solution C5 instead of the electrolytic solution of the conditions . FIG . 57 shows the charging/ discharging curve of present invention . the first cycle , and FIG . 58 shows the results of the rate capacity test . Comparative Example 2-5 ( 1 ) Current is supplied in a direction that causes occlusion 55 of lithium to the negative electrode . A negative electrode was produced similarly to Example ( 2 ) Voltage range: From 2 V down to 0.01 V ( v.s. Li / Li * ) 2-1 using a similar soft carbon as in Example 2-2 . A ( 3 ) Rate : 0.1C , 0.2C , 0.5C , 1C , 2C , 5C , 10C , and 0.1C nonaqueous electrolyte secondary battery of Comparative ( stop current after reaching 0.01 V ) . Example 2-5 was obtained similarly to that of Example 2-1 ( 4 ) Three measurements at each rate ( a total of 24 cycles ). 60 except for using this negative electrode and using electro Here , “ 1C ” represents a current value required for fully lytic solution C5 instead of the electrolytic solution of the charging or discharging a battery in 1 hour under constant present invention . current. Based on FIG . 57 , the nonaqueous electrolyte secondary Comparative Example 2-6 battery of Example 2-1 is obviously chargeable and dis- 65 chargeable. In addition , based on FIG . 58 , the nonaqueous A negative electrode was produced similarly to Compara electrolyte secondary battery of Example 2-1 is understood tive Example 2-2 . A nonaqueous electrolyte secondary bat