Carbonaceous electrode and compatible electrolyte

• US 5,643,695 A
• Filed: 04/10/1996
• Issued: 07/01/1997
• 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:
  US08/630,402
• Time in Patent Office: 447 Days
• Field of Search: 429/194, 429/196, 429/197, 429/223, 429/224, 429/218, 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 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0566 Liquid materials
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• CPC Class Codes: H01M 2300/004 Three solvents
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• 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 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• 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 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 4/623 fluorinated polymers
• CPC Class Codes: H01M 4/661 Metal or alloys, e.g. alloy coatings H01M4/669 take precedence
• CPC Class Codes: H01M 4/663 containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
• CPC Class Codes: H01M 4/667 in the form of layers, e.g. coatings
• 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

The inventions provides a battery which comprises a first electrode, a counter electrode which forms an electrochemical couple with said first electrode, and an electrolyte. The first electrode comprises 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 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 24 microns (μm). The electrolyte comprises a solvent mixture and a solute; the solvent mixture comprises (i) ethylene carbonate (EC), and (ii) a solvent selected from the group consisting of propylene carbonate (PC), butylene carbonate (BC), and mixtures thereof with the ethylene carbonate being present in an amount by weight which is at least as great as the amount of any other solvent. Optionally, the solvent mixture further comprises one or more other organic solvents selected from the group consisting of methyl ethyl carbonate (MEC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dimethyl carbonate (DMC), and mixtures thereof.

Claims

1. A battery 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 0.3350 to 0.3360 nanometers (nm), a crystallite size in the direction of c-axis (L_c) being greater than about 100 nanometers (nm) and less than about 200 nanometers (nm), a BET surface area of greater than about 6 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 16 microns (μ

m); and

b) 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), ethylene carbonate (EC), and optionally one or more other organic solvents having a boiling point less than the boiling of point of said EC;

with the ethylene carbonate being present in an amount by weight which is at least as great as the amount of propylene carbonate and at least as great as the amount of any said other solvent, respectively.

2. The battery according to claim 1 wherein said counter electrode comprises an intercalation active material;

and wherein said battery is further characterized by a first cycle capacity loss of less than about 25 percent of first cycle charge capacity and said first electrode further characterized by a reversible capacity of greater than about 330 milliamp hours per gram (mAh/g).

3. The battery according to claim 1 wherein said binder is polyvinylidene difluoride (PVDF).

4. The battery according to claim 1 wherein said one or more other organic solvents is selected from the group consisting of methyl ethyl carbonate (MEC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dimethyl carbonate (DMC), butylene carbonate (BC), and mixtures thereof.

5. The battery according to claim 1 wherein said solvent mixture further comprises dimethyl carbonate (DMC).

6. The battery according to claim 5 wherein said solvent mixture consists of said EC, PC, and DMC in a weight ratio of 1EC:

1PC;

1DMC to 2EC;

1PC;

1DMC.

7. A battery which comprises a first electrode, a counter electrode which forms an electrochemical couple with said first electrode, and an electrolyte:

a) said first electrode comprising 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 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 24 microns (μ

m); and

b) said electrolyte comprising a solvent mixture and a solute;

said solvent mixture comprising propylene carbonate (PC) and ethylene carbonate (EC), with the ethylene carbonate being present in an amount by weight which is at least as great as the amount of said propylene carbonate.

8. The battery according to claim 7 wherein said solvent mixture consists of EC and PC in a weight ratio of ethylene carbonate to propylene carbonate of 50EC:

50PC to 75EC;

25PC.

9. The battery according to claim 7 wherein said solvent mixture consists of said PC, and EC, and one or more other organic solvents different from said EC and said PC;

said one or more other organic solvents having a boiling point less than the boiling point of said EC.

10. The battery according to claim 9 wherein said one or more other organic solvents is selected from the group consisting of methyl ethyl carbonate (MEC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dimethyl carbonate (DMC), butylene carbonate (BC), and mixtures thereof.

11. The battery according to claim 10 wherein said ethylene carbonate is present in an amount not less than the amount by weight of said one or more other organic solvents.

12. The battery according to claim 7 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.

13. The battery according to claim 12 wherein said matrix is a polymeric acrylate.

14. The battery according to claim 12 wherein said matrix is porous polypropylene or porous polyethylene.

15. The battery according to claim 12 wherein said matrix is a glass fiber material.

16. The battery according to claim 7 wherein said first electrode is a negative electrode and said counter electrode is a positive electrode comprising a lithium transition metal oxide compound.

17. The battery according to claim 16 wherein said lithium transition metal oxide compound is selected from the group consisting of LiMn₂ O₄, LiNiO₂, LiCoO₂, LiNiVO₄, LiCoVO₄, LiCoNiO₂, and mixtures thereof.

18. The battery according to claim 7 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).

19. The battery according to claim 7 wherein the crystallite size (L_c) is greater than about 100 nanometers (nm).

20. The battery according to claim 7 wherein the crystallite size (L_c) is less than about 200 nanometers (nm).

21. A battery which comprises a first electrode, a counter electrode which forms an electrochemical couple with said first electrode, and an electrolyte:

a) said first electrode comprising 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 greater than about 90 nanometers (nm) and less than about 200 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 about 16 microns (μ

m); and

b) said electrolyte comprising a solute and a solvent mixture;

said solute comprising a salt of a metal;

said solvent mixture comprising (i) ethylene carbonate (EC), and (ii) a solvent selected from the group consisting of propylene carbonate (PC), butylene carbonate (BC), and mixtures thereof with the ethylene carbonate being present in an amount by weight which is at least as great as the amount of any other solvent.

22. The battery according to claim 21 wherein said solvent mixture consists of EC and PC in a weight ratio of ethylene carbonate to propylene carbonate of 50EC:

50PC to 75EC;

25PC.

23. The battery according to claim 21 wherein said solvent mixture further comprises one or more other organic solvents selected from the group consisting of methyl ethyl carbonate (MEC), diethyl carbonate (DEC), dipropyl carbonate (DPC), dimethyl carbonate (DMC), and mixtures thereof.

24. The battery according to claim 23 wherein said one or more other organic solvents consists of dimethyl carbonate (DMC).

25. The battery according to claim 24 wherein said EC, PC, and DMC are in a weight ratio of 1EC:

1PC;

1DMC to 2EC;

1PC;

1DMC.

26. The battery according to claim 21 wherein said solvent mixture consists of said EC and BC in a weight ratio of 50EC:

25BC to 75EC;

25BC.

27. The battery according to claim 21 wherein said electrolyte further comprises a separator in the form of a solid matrix forming a network with voids interpenetrated by said solvent and said solute.

28. The battery according to claim 21 wherein said first electrode is a negative electrode and said counter electrode is a positive electrode comprising a lithium transition metal oxide compound.

29. The battery according to claim 21 wherein said lithium transition metal is lithium manganese oxide.

30. The battery according to claim 21 wherein said EC is present in an amount by weight which is at least as great as the combined amount of any other solvents.