Carbonaceous electrode and compatible electrolyte solvent

• US 5,712,059 A
• Filed: 11/01/1996
• Issued: 01/27/1998
• Est. Priority Date: 09/26/1995
• Status: Expired due to Term

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Inventors: Barker, Jeremy, Gao, Feng
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/740,765
• Time in Patent Office: 452 Days
• Field of Search: 429/197, 429/223, 429/224, 429/218, 429/249.252, 429/217, 423/448
• US Class Current: 429/331
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• 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 50/417 Polyolefins
• CPC Class Codes: H01M 50/42 Acrylic resins
• CPC Class Codes: H01M 50/437 Glass
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A battery which comprises a first electrode and a counter electrode which forms an electrochemical couple with the first electrode, and an electrolyte. The first electrode comprises graphite particles and the electrolyte comprises a solvent mixture and a solute. The solvent mixture comprises vinylene carbonate (VC) or substituted derivatives thereof and propylene carbonate (PC).

Claims

1. An electrochemical cell which comprises a first electrode, a counter electrode which forms an electrochemical couple with said first electrode, and an electrolyte:

a. said first electrode consisting essentially of graphite particles and a binder, where on the basis of 100 parts by weight, said binder constitutes up to about 15 parts and said graphite particles constitute at least about 85 parts;

said graphite particles having an interlayer distance spacing of 002 planes (d₀₀₂) as determined by x-ray diffraction of 0.330 to 0.340 nanometers (nm), a crystallite size in the direction of c-axis (L_c) being at least about 90 nanometers (nm) and less than about 1000 nanometers (nm), a BET surface area of greater than about 4 square meters per gram (m² /g) and up to about 16 square meters per gram (m² /g), and at least 90 percent by weight of said graphite particles having a size less than 25 microns (μ

m); and

said electrolyte comprising a solute and a solvent mixture;

said solute consisting essentially of a salt of a metal;

said solvent mixture consisting essentially of propylene carbonate (PC), vinylene carbonate (VC) or a substituted derivative thereof, and optionally one or more other organic solvents;

with the propylene carbonate being present in an amount by weight which is not greater than the combined amount of said vinylene carbonate or its derivative and any said other solvent.

2. The electrochemical cell according to claim 1 wherein said solvent mixture consists of said VC or its derivative and said PC in a weight ratio of said vinylene carbonate or its derivative to said propylene carbonate of 80:

20 to 20;

80.

3. The electrochemical cell according to claim 2 wherein said one or more other organic solvents is selected from the group consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dibutyl carbonate (DBC), diethoxy ethane (DEE), ethyl methyl carbonate (EMC), butylene carbonate (BC), and mixtures thereof.

4. The electrochemical cell according to claim 1 wherein said solvent mixture further comprises ethylene carbonate (EC).

5. The electrochemical cell according to claim 4 wherein the relative amounts by weight of said VC or its derivative, said PC, and said EC are about the same.

6. An electrochemical cell which comprises a first electrode, a counter electrode which forms an electrochemical couple with said first electrode, and an electrolyte;

said first electrode comprising graphite particles, and said electrolyte comprising a solvent mixture and a solute;

said solvent mixture comprising vinylene carbonate (VC) or a substituted derivative thereof and propylene carbonate (PC).

7. The electrochemical cell according to claim 6 wherein said solvent mixture consists of said VC or its derivative and said PC in a weight ratio of said vinylene carbonate or its derivative to said propylene carbonate of 80:

20 to 20;

80.

8. The electrochemical cell according to claim 6 wherein said solvent mixture consists of said PC and said VC or its derivative, and one or more other organic solvents having a boiling point of about 80°

C. to about 300°

C. and forming a solute with lithium salts.

9. The electrochemical cell according to claim 8 wherein said one or more other organic solvents is selected from the group consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dibutyl carbonate (DBC), diethoxy ethane (DEE), ethyl methyl carbonate (EMC), butylene carbonate (BC), and mixtures thereof.

10. The electrochemical cell according to claim 8 wherein the relative amounts by weight of said solvents are selected to provide the amount of said PC being less than the combined about of said VC or its derivative and said one or more other solvents.

11. The electrochemical cell according to claim 6 wherein said solvent mixture further comprises ethylene carbonate (EC).

12. The electrochemical cell according to claim 11 wherein the relative amounts by weight of said VC or its derivative, said PC, and said EC are about the same.

13. The electrochemical cell according to claim 6 wherein said graphite particles have an interlayer distance spacing of 002 planes (d₀₀₂) as determined by x-ray diffraction of 0.330 to 0.340 nanometers (nm), a crystallite size in the direction of c-axis (L_c) being greater than about 90 nanometers (nm) and less than about 1000 nanometers, and at least 90 percent by weight of said graphite particles having a size less than about 25 microns (μ

m).

14. The electrochemical cell according to claim 13 wherein said graphite particles have a BET surface area greater than about 4 square meters per gram (m² /g) and up to about 16 meters square per gram (m² /g).

15. The electrochemical cell according to claim 13 wherein the crystallite size (L_c) is greater than about 100 nanometers (nm) and less than about 200 nanometers (nm).

16. The electrochemical cell according to claim 6 wherein said electrolyte further comprises a separator in the form of a solid matrix forming a network with voids interpenetrated by said solvent mixture and said solute.

17. The electrochemical cell according to claim 16 wherein said matrix is selected from the group consisting of polymeric acrylate, porous polypropylene, porous polyethylene, and glass fiber material.

18. The electrochemical cell according to claim 6 wherein said counter electrode comprises an intercalation active material.

19. The electrochemical cell according to claim 6 wherein said first electrode is a negative electrode and said counter electrode is a positive electrode comprising a lithium transition metal oxide compound.

20. The electrochemical cell according to claim 19 wherein said lithium transition metal oxide compound is selected from the group consisting of LiMn₂ O₄, LiNiO₂, LiCoO₂, LiNiVO₄, LiCoVO₄, LiCoNiO₂, and mixtures thereof.

21. The electrochemical cell according to claim 20 wherein said lithium transition metal is lithium manganese oxide.

22. The electrochemical cell according to claim 6 wherein said first electrode consists essentially of said graphite and a binder.

23. The electrochemical cell according to claim 22 wherein on a basis of 100 parts by weight, said binder constitutes up to about 15 parts and said graphite at least about 85 parts.

24. The electrochemical cell according to claim 6 wherein said substituted derivative of VC is obtained by replacing at least one hydrogen atom of said VC with a substituent selected from the group consisting of halogens and alkyls having 1 to 3 carbon atoms.

25. The electrochemical cell according to claim 11 wherein said VC or substituted derivative thereof has a melting point less than that of said EC.