Non-Aqueous Electrolyte Battery and Method of Manufacturing the Same

• US 20090286160A1
• Filed: 12/01/2006
• Published: 11/19/2009
• Est. Priority Date: 12/02/2005
• Status: Active Grant

• Current Assignee: GS Yuasa International Ltd. (GS Yuasa Corporation)
• Original Assignee: GS Yuasa Corporation
• Inventors: Yamate, Shigeki, Kozono, Suguru, Nukuda, Toshiyuki, Katayama, Yoshihiro, Tanaka, Ichiro, Tsumura, Naohiro
• Granted Patent: US 8,163,423 B2
• Time in Patent Office: Days
• US Class Current: 429/231.500
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making

Abstract

Gas generation of a non-aqueous electrolyte battery having a negative active material that intercalates/deintercalates lithium ions at a potential not lower than 1.2 V relative to the potential of lithium as negative electrode is suppressed.

A non-aqueous electrolyte battery comprising a non-aqueous electrolyte containing an electrolyte salt and a non-aqueous solvent, a positive electrode and a negative electrode is characterized in that the main active material of said negative electrode is an active material that intercalates/deintercalates lithium ions at a potential not lower than 1.2 V relative to the potential of lithium and the auxiliary active material of said negative electrode is an active material that at least intercalates lithium ions at a potential lower than 1.2 V relative to the potential of lithium and that there exists lithium showing a spin-lattice relaxation time (T₁) of not less than 1 second as determined by a solid-state Li—NMR measurement in the main active material of said negative electrode. A method of manufacturing a non-aqueous electrolyte battery containing a non-aqueous electrolyte, a positive electrode and a negative electrode (a main active material and an auxiliary active material of the negative electrode) is characterized in that the negative electrode potential is lowered to not higher than 0.8 V relative to the potential of lithium at least once in the initial cycle.

Claims

1-15. -15. (canceled)

16. A non-aqueous electrolyte battery comprising a non-aqueous electrolyte containing an electrolyte salt and a non-aqueous solvent, a positive electrode and a negative electrode, characterized in that the main active material of said negative electrode is an active material that intercalates/deintercalates lithium ions at a potential not lower than 1.2 V relative to the potential of lithium and the auxiliary active material of said negative electrode is a low temperature baked carbon material that at least intercalates lithium ions at a potential lower than 1.2 V relative to the potential of lithium and shows an interplanar spacing of the (002) plane of not less than 0.34 nm, a crystallite size Lc of not more than 100 nm as observed by wide-angle X-ray diffractometry, and a BET specific surface area of not more than 30 m²/g and that there exists lithium showing a spin-lattice relaxation time (T₁) of not less than 1 second as determined by a solid-state Li—

NMR measurement in the main active material of said negative electrode.

17. The battery according to claim 16, characterized in that a film coat having a carbonate structure exists in the surface of said negative electrode.

18. The battery according to claim 16, characterized in that the main active material of said negative electrode is spinel-type lithium titanate.

19. The battery according to claim 16, characterized in that lithium showing a spin-lattice relaxation time (T₁) of not less than 1 second as observed by a solid-state Li—

NMR measurement is made to exist in the main active material of said negative electrode by lowering the potential of the negative electrode to not higher than 0.8 V relative to the potential of lithium at least once before operating the non-aqueous electrolyte battery.

20. The battery according to claim 19, characterized in that the non-aqueous electrolyte battery is designed such that the potential of the positive electrode becomes not higher than 4.5 V relative to the potential of lithium when the potential of the negative electrode becomes not higher than 0.8 V relative to the potential of lithium.

21. The battery according to claim 16, characterized in that the collector of said negative electrode is copper, nickel or an alloy of them.

22. The battery according to claim 16, characterized in that the non-aqueous electrolyte battery is operated in a region of the potential of the negative electrode higher than 0.8 V relative to the potential of lithium.

23. A method of manufacturing a non-aqueous electrolyte battery containing a non-aqueous electrolyte containing an electrolyte salt and a non-aqueous solvent, a positive electrode and a negative electrode, characterized in that an active material that intercalates/deintercalates lithium ions at a potential not lower than 1.2 V relative to the potential of lithium is used for the main active material of said negative electrode and a low-temperature baked carbon material that at least intercalates lithium ions at a potential lower than 1.2 V relative to the potential of lithium and shows an interplanar spacing of the (002) plane of not less than 0.34 nm, a crystallite size Lc of not more than 100 nm as observed by wide-angle X-ray diffractometry, and a BET specific surface area of not more than 30 m²/g is used for the auxiliary active material of said negative electrode and that the potential of the negative electrode is lowered to not higher than 0.8 V relative to the potential of lithium at least once in the initial cycle.

24. The method according to claim 23, characterized in that lithium showing a spin-lattice relaxation time (T₁) of not less than 1 second as determined by a solid-state Li—

NMR measurement is made to exist in the main active material of said negative electrode by lowering the potential of the negative electrode to not higher than 0.8V relative to the potential of lithium at least once in the initial cycle.

25. The method according to claim 23, characterized in that a film coat having a carbonate structure is made to exist in the surface of said negative electrode by lowering the potential of the negative electrode to not higher than 0.8 V relative to the potential of lithium at least once in the initial cycle.

26. The method according to claim 23, characterized in that the main active material of said negative electrode is spinel-type lithium titanate.

27. The method according to claims 23, characterized in that the potential of the negative electrode is lowered to not higher than 0.8 V relative to the potential of lithium by raising the charging voltage above the operating voltage in the initial cycle.

28. The method according to claim 27, characterized in that the potential of the positive electrode is made to become not higher than 4.5 V relative to the potential of lithium when the potential of the negative electrode becomes not higher than 0.8 V relative to the potential of lithium.