US008932761 B2 (12) United States Patent (10) Patent No.: US 8,932,761 B2 Yamaguchi et al. (45) Date of Patent: *Jan. 13, 2015 (54) ANODE AND METHOD OF HOIM 4/1.31 (2010.01) MANUFACTURING THE SAME, AND HO1 M 4/134 (2010.01) BATTERY AND METHOD OF HOIM IO/O52 (2010.01) MANUFACTURING THE SAME (52) U.S. Cl. (75) Inventors: Hiroyuki Yamaguchi, Fukushima (JP); CPC H0IM 4/38 (2013.01); H0IM 4/13 (2013.01); H01 M 4/139 (2013.01); H0IM 4/366 Hiroshi Horiuchi, Fukushima (JP): (2013.01); H0IM 4/485 (2013.01); HOIM Kenichi Kawase, Fukushima (JP); 4/131 (2013.01); H01 M 4/134 (2013.01): HOIM Tadahiko Kubota, Fukushima (JP); 10/052 (2013.01); Y02E 60/122 (2013.01) Hideki Nakai, Fukushima (JP); USPC ........................................ 429/231.1; 429/233 Takakazu Hirose, Fukushima (JP) (58) Field of Classification Search (73) Assignee: Sony Corporation, Tokyo (JP) USPC .............. 429/218.1, 209, 233,236, 242, 221, 429/223, 229, 220; 204/291, 290.01 (*) Notice: Subject to any disclaimer, the term of this See application file for complete search history. patent is extended or adjusted under 35 U.S.C. 154(b) by 937 days. (56) References Cited This patent is Subject to a terminal dis U.S. PATENT DOCUMENTS claimer. 4,950,566 A 8/1990 Huggins et al. (21) Appl. No.: 11/995,802 5,696,206 A * 12/1997 Chen et al. .................... 525, 186 (22) PCT Filed: May 22, 2007 2004/009 1780 A1* 5/2004 Kinoshita et al. .......... 429,231.1 (86). PCT No.: PCT/UP2007/060401 FOREIGN PATENT DOCUMENTS S371 (c)(1), JP 59-157969 * 9, 1984 ............ HOM 10/12 (2), (4) Date: Jan. 15, 2008 JP 08-333603 * 12, 1996 ................ B22F1/OO (87) PCT Pub. No.: WO2007/136046 (Continued) OTHER PUBLICATIONS PCT Pub. Date: Nov. 29, 2007 (65) Prior Publication Data International Search Report dated Oct. 7, 2007. US 2009/0092892 A1 Apr. 9, 2009 Primary Examiner — Raymond Alejandro (74) Attorney, Agent, or Firm — Dentons US LLP (30) Foreign Application Priority Data (57) ABSTRACT May 23, 2006 (JP) ................................. 2006-142977 An anode wherein the anode active material layer includes May 23, 2006 (JP) ................................. 2006-142978 anode active material particles made of an anode active mate May 11, 2007 (JP) ................................. 2007-127005 rial including at least one of silicon and tin as an element. An May 11, 2007 (JP) ................................. 2007-127006 oxide-containing film including an oxide of at least one kind (51) Int. Cl. selected from the group consisting of silicon, germanium and HOLM 4/58 (2010.01) tin is formed in a region in contact with an electrolytic solu HOLM 4/38 (2006.01) tion of the surface of each anode active material particle. The HOLM 4/13 (2010.01) region in contact with the electrolytic solution of the surface HOLM 4/39 (2010.01) of each anode active material particle is covered with the HOLM 4/36 (2006.01) oxide-containing film. HOLM 4/485 (2010.01) 8 Claims, 8 Drawing Sheets a- 22B, 34B 22D, 34D 220, 34C 22A, 34A US 8,932,761 B2 Page 2 (56) References Cited JP 2004-171874 6, 2004 JP 2004-319469 11, 2004 JP 2005-26144 * 1 2005 ............ HO1M 12/06 FOREIGN PATENT DOCUMENTS JP 2005-317446 11, 2005 WO 2006/033358 3, 2006 JP 09-28902O * 11, 1997 .............. HO1 M 4/62 JP 2000-012018 1, 2000 * cited by examiner U.S. Patent Jan. 13, 2015 Sheet 1 of 8 US 8,932,761 B2 25 14 15A 15 ZZZZ17212121727-27.212127 A-1 4K) / WSZZY RN 4. N 6 727-721212 SS NYSAYYYYS 727-ZZZZY SN 17 N 12 11 O 1 2 NIK,NOEN,NOEN-ON-NOEN-NOEN-NOFSTIN 3 4. NÚ,ÍRÓ-ŠŒ-ÍÑIŠI?,?,TÍN NOENOESJTS,NOETSOENTSTSTONTST?OENTÍN 13 STY CZZZZZ& ZYZZYZZZZZZZY77Z Z24-4444 26 FIG.NN 1 NN U.S. Patent Jan. 13, 2015 Sheet 2 of 8 US 8,932,761 B2 U.S. Patent Jan. 13, 2015 Sheet 3 of 8 US 8,932,761 B2 FG. 3 U.S. Patent Jan. 13, 2015 Sheet 5 of 8 US 8,932,761 B2 e- 22B, 34B (AACS U.S. Patent Jan. 13, 2015 Sheet 6 of 8 US 8,932,761 B2 rN N 2213,2. O2, U.S. Patent Jan. 13, 2015 Sheet 7 of 8 US 8,932,761 B2 U.S. Patent Jan. 13, 2015 Sheet 8 of 8 US 8,932,761 B2 1600 1400 1200 1000 800 300 295 290 285 ENERGY (eV) FG. 9 US 8,932,761 B2 1. 2 ANODE AND METHOD OF coating film formed by a vapor-phase method, thereby suffi MANUFACTURING THE SAME, AND cient cycle characteristics cannot be obtained, so a further BATTERY AND METHOD OF improvement is desired. MANUFACTURING THE SAME In view of the foregoing, it is an object of the invention to provide an anode capable of improving charge-discharge effi TECHNICAL FIELD ciency and a method of manufacturing the anode, and a bat tery using the anode, and a method of manufacturing the The present invention relates to an anode including an battery. anode active material which includes at least one of silicon A first anode according to the invention is used in a battery 10 including a cathode, an anode and an electrolyte, and the (Si) and tin (Sn) as an element, and a method of manufactur anode includes: an anode current collector; and an anode ing the anode, and a battery and a method of manufacturing active material layer arranged on the anode current collector, the battery. wherein the anode active material layer includes anode active BACKGROUND ART material particles including at least one of silicon and tin as an 15 element, and each of the anode active material particles includes an oxide-containing film including an oxide of at In recent years, a large number of portable electronic least one kind selected from the group consisting of silicon, devices such as camcorders, digital still cameras, cellular germanium and tin in a region in contact with the electrolyte phones, personal digital assistances and laptop computers of its surface. In this case, the oxide-containing film is formed have been emerged, and an attempt to reduce the size and the by a liquid-phase method. weight of them has been made. Accordingly, the development A method of manufacturing an anode according to the oflightweight secondary batteries capable of obtaining a high invention is a method of manufacturing an anode used in a energy density as power sources for the electronic devices battery including a cathode, an anode and an electrolyte, and have been promoted. Among them, a lithium-ion secondary the method includes: a step of arranging an anode active battery using a carbon material for an anode, a composite 25 material layer including anode active material particles on an material of lithium (Li) and a transition metal for a cathode anode current collector, the anode active material particles and a carbonate for an electrolytic solution has been widely including at least one of silicon and tin; and a step of forming put to practical use, because the lithium-ion secondary battery an oxide-containing film including an oxide of at least one can obtain a larger energy density thana lead-acid battery and kind selected from silicon, germanium and tin in a region in a nickel-cadmium battery in related arts. 30 contact with the electrolyte of the surface of each of the anode Moreover, recently as the performance of portable elec active material particles by a liquid-phase method. tronic devices is enhanced, a further improvement in capacity A first battery according to the invention includes a cath is desired, and it is considered to use tin, silicon or the like as ode, an anode and an electrolyte, and the anode is the above an anode active material instead of a carbon material (for described anode according to the invention. Moreover, in a 35 method of manufacturing a battery according to the invention, example, refer to Patent Literature 1). It is because the theo an anode is manufactured by the above-described method of retical capacity of tin, 994 mAh/g, and the theoretical capac manufacturing an anode according to the invention. ity of silicon, 4199 mAh/g are much larger than the theoretical In the first anode and the first battery according to the capacity of graphite, 372 mAh/g, so an increase in capacity invention, the oxide-containing film is formed in a region in can be expected. 40 contact with the electrolyte of the surface of each anode active However, a tin alloy or a silicon alloy into which lithium is material particle by a liquid-phase method, so the region in inserted has high activity, so there is an issue that an electro contact with the electrolyte of the surface of each anode active lytic Solution is easily decomposed, and lithium is inacti material particle can be uniformly covered with the oxide vated. Therefore, when charge and discharge are repeated, containing film, and chemical stability can be improved. charge-discharge efficiency declines, thereby sufficient cycle 45 Therefore, in the battery using the anode, charge-discharge characteristics cannot be obtained. efficiency can be improved. Therefore, it is considered to form an inert layer on a In the method of manufacturing an anode and the method Surface of an anode active material, and, for example, it is of manufacturing a battery according to the invention, the proposed to form a coating film of silicon oxide on a Surface oxide-containing film is formed by a liquid-phase method, so of an anode active material (for example, refer to Patent 50 the oxide-containing film can be formed in the interior, which Literature 2).