Rechargeable positive electrode

• US 5,523,179 A
• Filed: 11/23/1994
• Issued: 06/04/1996
• Est. Priority Date: 11/23/1994
• Status: Expired due to Term

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Chu, May-Ying
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US08/344,384
• Time in Patent Office: 559 Days
• Field of Search: 429/218, 429/212, 429/213, 429/233, 429/192, 429/190, 429/194, 429/104, 429/102, 429/103, 429/105, 136/238, 136/263
• US Class Current: 429/104
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/36 Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 10/39 working at high temperature
• CPC Class Codes: H01M 10/3909 Sodium-sulfur cells
• CPC Class Codes: H01M 10/44 Methods for charging or discharging circuits for charging H02J7/00
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0409 by a doctor blade method, slip-casting or roller coating
• CPC Class Codes: H01M 4/0411 by extrusion
• CPC Class Codes: H01M 4/0414 by screen printing
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/0421 involving vapour deposition
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/043 involving compressing or compaction
• CPC Class Codes: H01M 4/0435 : Rolling or calendering
• CPC Class Codes: H01M 4/13 : Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/38 : of elements or alloys
• CPC Class Codes: H01M 4/382 : Lithium H01M4/405 takes precedence
• CPC Class Codes: H01M 4/581 : Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/5815 : Sulfides
• CPC Class Codes: H01M 4/60 : of organic compounds
• CPC Class Codes: H01M 4/621 : Binders
• CPC Class Codes: H01M 4/624 : Electric conductive fillers
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/626 : Metals
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 6/168 : by additives
• CPC Class Codes: H01M 6/18 : with solid electrolyte
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 6/188 : Processes of manufacture
• CPC Class Codes: H01M 6/40 : Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making
• CPC Class Codes: Y10T 29/49115 : including coating or impregnating

Abstract

Disclosed are battery cells comprising a sulfur-based positive composite electrode. Preferably, said cells are secondary cells, and more preferably thin film secondary cells. In one aspect, the cells can be in a solid-state or gel-state format wherein either a solid-state or gel-state electrolyte separator is used. In another aspect of the invention, the cells are in a liquid format wherein the negative electrode comprises carbon, carbon inserted with lithium or sodium, or a mixture of carbon with lithium or sodium. The novel battery systems of this invention have a preferred operating temperature range of from -40° C. to 145° C. with demonstrated energies and powers far in excess of state-of-the-art high-temperature battery systems.

Claims

1. A battery cell which comprises:

a) a positive electrode comprising a mixture of

i) between about 20% to about 80% active-sulfur in percent by weight;

ii) a gel-state or solid-state ionically conductive material in percent by weight between about 15% to 75%; and

iii) an electronically conductive material in a percent by weight between about 5% and about 40%;

the mixture having between about 10% and about 100% of the active-sulfur accessible to any charge carriers;

b) a current collector electrically connected to the positive electrode;

c) a negative electrode; and

d) an electrolyte separator;

wherein the active-sulfur is elemental sulfur or sulfur-containing discharge products of elemental sulfur.

2. The battery cell of claim 1 wherein the electrolyte separator is a solid-state electrolyte separator.

3. The battery cell of claim 1 wherein the electrolyte separator is a gel-state electrolyte separator.

4. The battery cell of claim 1 wherein the electrolyte separator is a liquid electrolyte separator.

5. The battery cell of claim 1 wherein the negative electrode is a solid-state negative electrode.

6. The battery cell of claim 1 wherein the negative electrode is a gel-state negative electrode.

7. The battery cell of claim 1 wherein the negative electrode is a liquid negative electrode.

8. A battery cell according to claim 1 wherein the positive electrode is provided in a solid-state form.

9. A battery cell according to claim 8 wherein the negative electrode is selected from the group consisting of lithium, sodium, Na₄ Pb, lithium-silicon and lithium-aluminum alloys.

10. A battery cell according to claim 8 wherein the negative electrode is carbon or a metal/carbon material.

11. A battery cell of claim 10 wherein the electrolyte separator includes a liquid or gel-state electrolyte.

12. A battery cell according to claim 1 wherein the cell is operated at a temperature of at most about 180°

C., and wherein the positive electrode has between about 50% and about 100% of the active-sulfur accessible to any charge carriers.

13. A battery cell according to claim 1 wherein the ionically conductive material comprises a compound selected from the group consisting of polyether compounds, polyimine compounds, polythioether compounds, polyphosphazene compounds, polyalkylene oxide compounds, polyethylene oxide compounds, amorphous polyethylene oxide compounds, and combinations thereof.

14. A battery cell according to claim 1 wherein said electrolyte separator is a gel-state electrolyte separator comprising at least 20% by weight of an aprotic organic liquid immobilized by the presence of a gelling agent.

15. A battery cell according to claim 14 wherein the aprotic organic liquid is selected from the group consisting of sulfolane compounds, dimethyl sulfone compounds, tetrahydrofuran compounds, propylene carbonate compounds, dialkyl carbonate compounds, ethylene carbonate compounds, dimethyl carbonate compounds, butyrolactone compounds, N-methylpyrrolidinone compounds, tetramethylurea compounds, dioxolane compounds, glyme compounds, ether compounds, crown ether compounds, dimethoxyethane compounds, and combinations thereof.

16. A battery cell according to claim 14 wherein said gelling agent is selected from the group consisting of polyvinylidine fluoride compounds, hexafluropropylene-vinylidene fluoride copolymers, polyacrylonitrile compounds, cross-linked polyether compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and combinations thereof.

17. A battery cell according to claim 1 wherein positive electrode further comprises one or more of the following;

binders, electrocatalysts, surfactants, dispersants, and protective layer forming additives.

18. A battery cell according to claim 1 wherein the positive electrode includes

(a) the active-sulfur in a percentage by weight from about 30-75%,

(b) the ionically conductive material in percentage by weight form about 15 to 60%;

and

(c) the electronically conductive material in a percentage by weight from about 10-30%.

19. A battery cell according to claim 1 wherein the positive electrode includes

(a) the active-sulfur in a percentage by weight from about 40-60%,

(b) the ionically conductive material in percentage by weight form about 25-45%;

and

(c) the electronically conductive material in a percentage by weight from about 15-25%.

20. A battery cell of claim 19 wherein the positive electrode further comprises one or more of the following:

binders, electrocatalysts, surfactants, dispersants, and protective layer forming additives.

21. A battery cell of claim 20 wherein the electrolyte separator is a gel-state separator including polyethylene oxide or amorphous polyethylene oxide, and wherein the negative electrode is lithium or a lithium alloy.

22. A battery of claim 21 wherein the electrolyte separator is a solid-state separator including polyethylene oxide or amorphous polyethylene oxide, and wherein the negative electrode is lithium or a lithium alloy.

23. A battery cell which comprises:

(a) a positive composite electrode comprising active-sulfur in a percentage by weight from 20% to 80%, an ionically conductive material in a percentage by weight from 15% to 75%, and an electronically conductive material in a percentage by weight from 5% to 40%, the positive composite having between about 10% and about 100% of the active-sulfur accessible to any charge carriers;

(b) a negative electrode; and

(c) a solid-state electrolyte separator or a gel-state electrolyte separator;

wherein the active-sulfur is elemental sulfur or sulfur-containing discharge products of elemental sulfur.

24. A battery cell according to claim 23 wherein the positive electrode comprises

a) the active-sulfur in a percentage by weight from 30% to 75%;

b) the ionically conductive material in a percentage by weight from 15% to 60%; and

c) the electronically conductive material in a percentage by weight from 10% to 30%.

25. A battery cell according to claim 23 wherein said negative electrode is selected from the group consisting of alkali metals, alkaline earth metals, transition metals, mixtures of alkali, alkaline earth and transition metals, carbon, carbon inserted with lithium or sodium, and mixtures of carbon with lithium or sodium.

26. A battery cell according to claim 25 wherein said electrolyte separator is a gel-state electrolyte separator comprising at least 20% by weight of an aprotic organic liquid immobilized by the presence of a gelling agent.

27. A battery cell according to claim 26 wherein the aprotic orgainic liquid is selected from the group consisting of sulfolane compounds, dimethyl sulfone compounds, tetrahydrofuran compounds, propylene carbonate compounds, dialkyl carbonate compounds, ethylene carbonate compounds, dimethyl carbonate compounds, butyrolactone compounds, N-methylpyrrolidinone compounds, tetramethylurea compounds, dioxolane compounds, glyme compounds, ether compounds, crown ether compounds, dimethoxyethane compounds, and combinations thereof.

28. battery cell according to claim 26 wherein said gelling agent is selected from the group consisting of polyvinylidine fluoride compounds, hexafluropropylene-vinylidene fluoride copolymers, polyacrylonitrile compounds, cross-linked polyether compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and combinations thereof.

29. A battery cell according to claim 25 wherein said electrolyte separator is a solid-state electrolyte separator selected from the group consisting of ceramic electrolytes, polymeric electrolytes, glass electrolytes, beta alumina compounds, porous membranes and combinations thereof.

30. A battery cell according to claim 25 wherein said negative electrode is lithium, sodium, a mixture of carbon with lithium or sodium, or carbon inserted with lithium or sodium;

wherein the positive electrode comprises

a) the active-sulfur in a percentage by weight from 30% to 75%;

b) the ionically conductive material is a polyalkylene oxide in a percentage by weight from 15% to 60%; and

c) the electronically conductive material is in a percentage by weight from 10% to 30%.

31. A battery cell according to claim 30 wherein the positive electrode comprises

a) the active-sulfur in a percentage by weight from 40% to 60%;

b) the ionically conductive material is either amorphous or conventional polyethylene oxide and is in a percentage by weight from 25% to 45; and

c) the electronically conductive material is selected from the group consisting of carbon black, electronically conductive compounds having conjugated carbon-carbon, or both, carbon-nitrogen double bonds, electronically conductive polymers, polyaniline compounds, polythiophene compounds, polyacetylene compounds, polypyrrole compounds, combinations of carbon black and such electronically conductive compound or compounds, and combinations of such electronically conductive compounds; and

wherein said electronically conductive material is in a percentage by weight from 15% to 25%.

32. A battery cell according to claim 31 wherein said negative electrode comprises Li_y C₆ wherein y=0.3 to 2;

and wherein said electronically conductive material is carbon black.

33. A battery cell according to claim 32 wherein the electrolyte separator is a gel-state.

34. A battery cell according to claim 32 wherein the electrolyte separator is solid-state.

35. A battery cell according to claim 25 wherein said negative electrode is selected from the group consisting of lithium, sodium, Na₄ Pb, lithium-silicon and lithium-aluminum alloys.

36. A battery cell according to claim 23 wherein the negative electrode is provided in a solid-state form.

37. A battery cell according to claim 23 wherein the positive composite electrode is provided in a solid-state form.

38. A battery cell according to claim 23 wherein the negative electrode includes a material selected from the group consisting of metals, carbon, and metal/carbon material.

39. A battery cell according to claim 23 wherein the cell is operated at a temperature of at most about 180°

C.

40. A battery cell according to claim 23 wherein the ionically conductive material comprises a compound selected from the group consisting of polyether compounds, polyimine compounds, polythioether compounds, polyphosphazene compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and amorphous polyethylene oxide compounds, combinations thereof.

41. A battery cell of claim 23 wherein positive electrode further comprises one or more of the following:

binders, electrocatalysts, surfactants, dispersants, and protective layer forming additives.

42. A battery cell which comprises:

(a) a negative electrode which comprises carbon, carbon inserted with lithium or sodium, or a mixture of carbon with lithium or sodium; and

(b) a positive composite electrode comprising active-sulfur in a percentage by weight of from 20% to 80%, an ionically conductive material in a percentage weight of from 15% to 75%, and an electronically conductive material in a percentage by weight from 5% to 40%, wherein the positive composite electrode has between about 10% mid about 100% of the active-sulfur accessible to any charge carriers, and wherein the active-sulfur is elemental sulfur or sulfur-containing discharge products of elemental sulfur.

43. A battery cell according to claim 42 further comprising an electrolyte salt in a liquid electrolyte.

44. A battery cell according to claim 43 further comprising a separator within said liquid electrolyte.

45. A battery cell according to claim 44 wherein said separator includes a gelling agent selected from the group consisting of polyvinylidine fluoride compounds, hexafluropropylene-vinylidene fluoride copolymers, polyacrylonitrile compounds, cross-linked polyether compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and combinations thereof.

46. A battery cell according to claim 42 wherein said negative electrode comprises lithium inserted within highly disordered carbons, graphite intercalation compounds, or Li_y C₆ wherein y=0.3 to 2.

47. A battery cell according to claim 42 wherein said active-sulfur is in a percentage by weight from 30% to 75%;

wherein said ionically conductive material is in a percentage by weight from 15% to 60%; and

wherein said electronically conductive material is in a percentage by weight from 10% to 30%.

48. A battery cell according to claim 42 wherein said active-sulfur is in a percentage by weight from 40% to 60%;

wherein said ionically conductive material is a polyalkylene oxide in a percentage by weight from 25% to 45%; and

wherein said electronically conductive material is in a percentage by weight from 15% to 25%.

49. A battery cell according to claim 42 wherein the positive and negative electrodes are immersed in an aprotic organic liquid electrolyte.

50. A battery cell according to claim 49 wherein the aprotic organic liquid is selected from the group consisting of sulfolane compounds, dimethyl sulfone compounds, tetrahydrofuran compounds, propylene carbonate compounds, dialkyl carbonate compounds, ethylene carbonate compounds, dimethyl carbonate compounds, butyrolactone compounds, N-methylpyrrolinone compounds, tetramethylurea compounds, dimethoxyethane dioxolane compounds, glyme compounds, ether compounds, crown ether compounds, dimethoxyethane compounds, and combinations thereof.

51. A battery cell according to claim 42 wherein the negative electrode is provided in a solid-state form.

52. A battery cell according to claim 42 wherein the positive composite electrode is provided in a solid-state form.

53. A battery cell according to claim 42 wherein the ionically conductive material comprises a compound selected from the group consisting of polyether compounds, polyimine compounds, polythioether compounds, polyphosphazene compounds, polyalkylene oxide compounds, polyethylene oxide compounds, and amorphous polyethylene oxide compounds, and combinations thereof.

54. A battery cell of claim 42 wherein positive electrode further comprises one or more of the following:

binders, electrocatalysts, surfactants, dispersants, and protective layer forming additives.

55. A battery cell which comprises:

a) a positive electrode consisting essentially of a mixture of

i) between about 20% to about 80% active-sulfur in percent by weight;

ii) a gel-state or solid-state ionically conductive material in percent by weight between about 15% to 75%; and

iii) an electronically conductive material in a percent by weight between about 5% and about 40%;

the mixture having between about 10% and about 100% of the active-sulfur accessible to any charge carriers;

b) a current collector electrically connected to the positive electrode;

c) a negative electrode; and

d) an electrolyte separator;

wherein the active-sulfur is elemental sulfur or sulfur-containing discharge products of elemental sulfur.

56. The battery cell of claim 55 wherein the electrolyte separator is a solid-state or gel-state electrolyte separator.

57. The battery cell of claim 55 wherein the electrolyte separator is a liquid electrolyte separator.

58. The battery cell of claim 55 wherein the negative electrode is a solid-state or a gel-state negative electrode.

59. A battery cell according to claim 55 wherein the positive electrode comprises

a) the active-sulfur in a percentage by weight from 30% to 75%;

b) the ionically conductive material in a percentage by weight from 15% to 60%; and

c) the electronically conductive material in a percentage by weight from 10% to 30%.

60. A battery cell according to claim 55 wherein said negative electrode is selected from the group consisting of alkali metals, alkaline earth metals, transition metals, mixtures of alkali, alkaline earth and transition metals, carbon, carbon inserted with lithium or sodium, and mixtures of carbon with lithium or sodium.

61. A battery cell according to claim 60 wherein the negative electrode is selected from the group consisting of lithium, sodium, Na₄ Pb, lithium-silicon and lithium-aluminum alloys.