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Hemumurta Unhau HEMUMURTAUS 20170365883A1UNHAU ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2017/ 0365883 A1 Luski et al. ( 43) Pub . Date : Dec . 21 , 2017 ( 54 ) LITHIUM ION BATTERY ( 52 ) U . S . CI. CPC .. HOIM 10 / 4235 ( 2013 .01 ) ; HOIM 10 /0525 (71 ) Applicants :GM GLOBAL TECHNOLOGY ( 2013 .01 ) ; HOIM 2 / 1653 ( 2013 .01 ) ; HOIM OPERATIONS LLC , DETROIT , MI 2 / 166 (2013 .01 ) (US ) ; Bar - Ilan University , Ramat Gan ( IL ) ( 57 ) ABSTRACT (72 ) Inventors : Shalom Luski, Rehovot ( IL ) ; Doron Aurbach , Bnei Brak ( IL ) ; Bob R . A lithium ion battery includes a positive and a negative Powell, JR ., Birmingham , MI (US ) ; Ion electrode , and a nanoporous or microporous polymer sepa C . Halalay , Grosse Pointe Park , MI rator soaked in electrolyte solution and disposed between the (US ) ; Timothy J . Fuller, Pittsford , NY electrodes . At least two different chelating agents are (US ) ; Anjan Banerjee , West Bengal included and selected to complex with : i ) two or more State ( IN ) ; Baruch Ziv , Ramat -Gan different transition metal ions ; ii ) a transition metal ion in ( IL ) ; Yuliya Shilina , Bat Yam ( IL ) two or more different oxidation states ; or iii ) both i ) and ii ) . The at least two different selected chelating agents are to (21 ) Appl. No. : 15 / 186 , 526 complex with transition metal ions in a manner sufficient to (22 ) Filed : Jun . 19 , 2016 not affect movement of lithium ions across the separator during operation of the battery . The chelating agents are : Publication Classification dissolved or dispersed in the electrolyte solution ; grafted (51 ) Int . Cl. onto the polymer of the separator ; attached to the binder HOIM 10 /42 ( 2006 . 01 ) material of the negative and /or positive electrode; disposed HOIM 2 / 16 ( 2006 .01 ) within pores of the separator ; coated on a surface of the HOIM 10 /0525 ( 2010 . 01 ) separator ; and /or coated on a surface of an electrode. bewonn 16 Botennnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnn Patent Application Publication Dec . 21 , 2017 Sheet 1 of 11 US 2017 /0365883 A1 SLOVENSKOcesti 16 . Fig - 1 . By 24 r16 wwwwwwwwwwwwwwww DEASTNSFX 1177 Fig - 2 .14 24 postane 129615 OD , , o Fig - 3 21 Patent Application Publication Dec. 21 , 2017 Sheet 2 of 11 US 2017 / 0365883 A1 AF IT IS EE EEE - F I I ME: EX EA A TE I TE : 3 EEG I TE : 3 IX e . de14a O O Or CO 16.armenn 13 Fig-4 . ??? : ??5 ? . : ) owin tu. con for . 15-22-23/1- 12 & : : 22 Patent Application Publication Dec . 21, 2017 Sheet 3 of 11 US 2017 /0365883 Al - -- - - -- - .. .. .. Pease 122 16 A RESEAA - WAAAAEAEAAAAAAAAAA ENG . vie aea1 0S % res12a Patent Application Publication . Dec . 21, 2017 Sheet 4 of ll US 2017/ 0365883 Al *ff or ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? * ????????????? ??. a real ta: Tax : - ra ra as a ra : = = = = = = = = = = = = = = 3 . = = = = = = = = t , |- - - - ??? .. [ ???? * - - - ! - ! - - - Fig-6 t - * ???? * ( ## 444 - ?????? - - - CSSED - ?????S * * * ?? - - - Patent Application Publication Dec . 21 , 2017 Sheet 5 of 11 US 2017 /0365883 A1 MUXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXXX . O Mn2* STANDARDS lu zl. LMO (SUPPLIER A ) 4 LMO ( SUPPLIER B ) * SPECTRUM * 0-06 . * TEGRATED * YA "YT7* 1 10 100 1000 IDAL9993 18 Fig - 7 Patent Application Publication Dec. 21 , 2017 Sheet 6 of 11 US 2017 / 0365883 A1 AUS & 3 A & TOTAL AMOUNTURO6 OF LEACHEDcoloco MMANGANESE osco * - LMO (SUPPLIER A ) * * * - LMO (SUPPLIER B ) * yungannynungunjenjejunywayuunganpengunningerneer EPIRRITX:< TOTALMANGANESE(ppm) beenforretninebonnebienestar M abasehas - - mm . brandmandando - verting TIMEGODOO (WEEKS ) Fig - 8A MOUNT IN SOLUTION 8 2 :EEEEE en Mn*FRACTION(%) wanganpurnaangerangsangandannyamanuntunganmengunjungan LMO (SUPPLIER A ) 22:ETEETEE 1 LMO (SUPPLIER B ) EEEEEE & - 0 wanyenyurungmannafinessomos 0 1 2 3 6 7 8 9 E Soo 800 [Fig 1980 - 8B Patent Application Publication Dec . 21 , 2017 Sheet 7 of 11 US 2017 /0365883 A1 namanya LNMOA) LNMO ( B ) pannungsmuspanna - - - NHÀ ? w TOTALMANGANESE(ppm) ??? ???????? Jum websitep equenas - -* mennes andetmed ton Od 2 3 5 6 7 8 9 TIMEE (WEEKS E E ) Fig - 9A 8 + + + + + + + + + + + + + + + + + + + + + + + + + + + + w - LNMO (A ) LNMO ( B ) 1 wwwdu wa Mn34FRACTION(%) S w TIME (WEEKS E E ) IFig* - 9B Patent Application Publication Dec . 21 , 2017 Sheet 8 of 11 US 2017 /0365883 A1 y a 4 . 2 V 3. 0 V AVA pepeepopeyasepp* XXXXXXXXXXXXXXXXXXXX fremmerneomenanana mgLMO)PERugGRAPHITE(ONMn humano me - fanmmwamb GRAPHI det omes for - frameborde at H 08 udbubuh poxy AS A * 4 EXPERIMENTDURATION (WEEKS3 * ) [Fig. - 10A . 4 . V moet . - 3 .0 V . - CYCLING end . E . butI do . E . glemmerutama KI ko . 0 .00 WEEKENAK MANUAL mu * EXPERIME k Fig - 10B Patent Application Publication Dec . 21 , 2017 Sheet 9 of 11 US 2017 /0365883 A1 REPLACEMENT SHEET P037087 -RD - SDJ GM Global Technology Operations LLC O ESR DATA trafik w O AAS DATA end nnnnntilLondo . tel MnCONCENTRATIONBYAAS(opm) TragacapeTragegewe y=0 .0328 +0 ,0688 , *R2* =0. 9998 n Lulian www Á= 066 +60 * 26 686808 html . nimmerinnemannprisma vanilin n monthlonmake the for fit ! 000 CALCULATED Mn2 * CONCENTRATION (ppm ) 2990000999999998899090goweDILI - IL Patent Application Publication Dec . 21 , 2017 Sheet 10 of 11 US 2017 /0365883 A1 OL Widd Ma2 + 1 ppm W 500 ppm wwwwwwwwwwwwwwwwwww 000 the EPRSIGNAL EKEWYNVTDota 200 ppm Agent 100 ppm 75 ppm W ond 5 pp , Unfort 25 ppm To pom spøm wwwwwwwwwwwww 1 pm wwwwwwwwwwwwwwwwwwvYX* wwww WWWWWWXXXXXXXXXXXXXXXXXXXXXX 1000 2000 3000 4000 5000 6000 MAGNETIC FIELD (G ) IFigi - 12A Mn24 SOCOCCUS JoWK29900000000 doooooo . 3 sho ope.ShowXX sines h 1000 2000 3000 4000 5000 6000 MAGNETIC FIELD (G ) Figi - 12B Patent Application Publication Dec . 21 , 2017 Sheet 11 of 11 US 2017 /0365883 A1 yourpayung YYYYYYYYYYYYYYYYY LANTARAS ?????? O Mn2 CALIBRATION ????????A 4. 2 V HOLDS $ 3. 0 V HOLDS XXXWWWWWWWWWWWWXXXXXXXXXXXXXX unape V CYCLING WWWINTEGRATEDEPR + + + + + + + + + + + + + + + + aao 1 quyuyam 0. RDDDAD * YTTTTT YTYT 1000 TOTAL M . BY AAS ( ppm Fig - 13A pamamen 8weitherrethanandammontandouthermettono Varamenn harmowe accommodo . Mn*FRACTION(%) - 42 V mengine 3. 0 V wannarriberendenwahrenwerkwentowe - CYCLINGxoood - EXPERIMENT DURATION (WEEKS ) IFig - 13B US 2017 /0365883 A1 Dec . 21, 2017 LITHIUM ION BATTERY [0006 ] FIG . 2 is a schematic , cross - sectional view of an example of a porous separator including a porous membrane TECHNICAL FIELD coated with a porous film of an example of a polymeric chelating agent disclosed herein ; [0001 ] The present disclosure relates generally to lithium [0007 ] FIG . 3 is a schematic , cross - sectional view of an ion batteries. example of a positive electrode including a structure coated with a porous film of an example of a polymeric chelating BACKGROUND agent disclosed herein ; [ 0002 ] Secondary , or rechargeable , lithium ion batteries [ 0008 ] FIG . 4 is a schematic , perspective view of an are used in many stationary and portable devices , such as example of a lithium ion battery during a discharging state , those encountered in the consumer electronic , automobile , where the porous separator of the battery includes an and aerospace industries . The lithium ion class of batteries example of the chelating agent disclosed herein ; has gained popularity for various reasons including a rela [0009 ] FIG . 5 is a schematic , perspective view of another tively high energy density , a general lack of any memory example of a lithium ion battery during a discharging state , effect when compared to other kinds of rechargeable batter where the separator of the battery includes a porous mem ies , a relatively low internal resistance , and a low self brane coated with a porous film of an example of the discharge rate when not in use . The ability of lithium polymeric chelating agent disclosed herein ; batteries to undergo repeated charging - discharging cycling [0010 ] FIG . 6 is a schematic , perspective view of yet over their useful lifetimes makes them an attractive and another example of a lithium ion battery during a discharg ing state , where an electrode ( s ) of the battery includes a dependable electrical energy source . structure coated with a porous film of an example of the polymeric chelating agent disclosed herein ; SUMMARY 10011 ] FIG . 7 is a graph showing the correlation between [ 0003 ] A lithium ion battery includes a positive electrode the integrated Electronic Paramagnetic Resonance (EPR ) including a binder material, a negative electrode including a spectra ( Y -axis ) and the total concentrations of manganese binder material, and a nanoporous or microporous polymer ions (measured by Atomic Absorption Spectroscopy (AAS ) , separator soaked in an electrolyte solution , the nanoporous in ppm ) for a set of Mn2 + reference solutions, compared to or microporous polymer separator being operatively dis the same correlation for the manganese cations dissolved posed between the positive electrode and the negative elec from two Li, Mn204 (LMO ) powders ; trode . At least two different chelating agents are included in [0012 ] FIG . 8A is a graph showing total manganese the battery and selected to complex with : i ) two or more amounts ( in ppm , Y -axis ) dissolved at 50° C . from the two different transition metal ions; ii ) a transition metal ion in Li Mn 04 (LMO ) powders into a 1M LiPF /EC :DMC ( 1 : 1 ) two or more different oxidation states ; or iii ) both i ) and ii ) . electrolyte solution
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