High performance energy storage devices

• US 20070104981A1
• Filed: 09/16/2004
• Published: 05/10/2007
• Est. Priority Date: 09/18/2003
• Status: Active Grant

• Current Assignee: Commonwealth Scientific & Industrial Research Organisation (Commonwealth Of Australia As Represented By Department Of Industry, Innovation, Climate Change, Science, Research And Tertiary Education)
• Original Assignee: Commonwealth Scientific & Industrial Research Organisation (Commonwealth Of Australia As Represented By Department Of Industry, Innovation, Climate Change, Science, Research And Tertiary Education)
• Inventors: Rano, David, Lam, Lan, Haigh, Nigei, Phyland, Christopher
• Granted Patent: US 7,923,151 B2
• Time in Patent Office: Days
• US Class Current: 429/7
• CPC Class Codes: H01G 11/04 Hybrid capacitors
• CPC Class Codes: H01G 11/30 characterised by their material
• CPC Class Codes: H01G 11/38 Carbon pastes or blends; Binders or additives therein
• CPC Class Codes: H01G 11/46 Metal oxides
• CPC Class Codes: H01G 11/58 Liquid electrolytes
• CPC Class Codes: H01M 10/12 Construction or manufacture
• CPC Class Codes: H01M 14/00 Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
• CPC Class Codes: H01M 16/00 Structural combinations of different types of electrochemical generators
• CPC Class Codes: H01M 4/583 Carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/627 Expanders for lead-acid accumulators
• CPC Class Codes: H01M 50/541 for lead-acid accumulators
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A lead-acid battery comprising: at least one lead-based negative electrode; at least one lead dioxide-based positive electrode; at least one capacitor electrode; and electrolyte in contact with the electrodes; wherein a battery part is formed by the lead based negative electrode and the lead dioxide-based positive electrode; and an asymmetric capacitor part is formed by the capacitor electrode and one electrode selected from the lead based negative electrode and the lead-dioxide based positive electrode; and wherein all negative electrodes are connected to a negative busbar, and all positive electrodes are connected to a positive busbar. The capacitor electrode may be a capacitor negative electrode comprising carbon and an additive mixture selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth, or a capacitor negative electrode comprising carbon, red lead, antimony in oxide, hydroxide or sulfate form, and optionally other additives. The capacitor electrode may be used in asymmetric capacitors and batteries of other types.

Claims

1. A lead-acid battery comprising:

at least one lead-based negative electrode;

at least one lead dioxide-based positive electrode;

at least one capacitor electrode; and

electrolyte in contact with the electrodes;

wherein a battery part is formed by the lead based negative electrode and the lead dioxide-based positive electrode; and

an asymmetric capacitor part is formed by the capacitor electrode and one electrode selected from the lead based negative electrode and the lead-dioxide based positive electrode; and

wherein all negative electrodes are connected to a negative busbar, and all positive electrodes are connected to a positive busbar.

2. The lead-acid battery of claim 1, wherein the electrodes alternate between positive and negative electrodes.

3. The lead-acid battery of claim 1, wherein the capacitor electrode comprises a high surface area material selected from carbon, ruthenium oxide, silver oxide, cobalt oxide and conducting polymers.

4. The lead-acid battery of claim 3, wherein the high surface area material is a high surface area carbon material.

5. The lead-acid battery of claim 4, wherein the high surface area material is activated carbon.

6. The lead-acid battery of claim 5, wherein the activated carbon material has a surface area of between 1000 and 2500 m²/g.

7. The lead-acid battery of claim 4, wherein the capacitor electrode further comprises carbon black.

8. The lead-acid battery of claim 7, wherein the capacitor electrode comprises a coating comprising between 5-20% carbon black, 40-80% activated carbon, 0-10% carbon fibres, and 5-25% binder.

9. The lead-acid battery of claim 1, wherein the lead-acid battery comprises at least one capacitor negative electrode comprising a high surface area active material and an additive or additive mixture comprising an oxide, hydroxide or sulfate of lead, zinc, cadmium, silver and bismuth, or a mixture thereof.

10. The lead-acid battery of claim 9, wherein the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.

11. The lead-acid battery of claim 9, wherein the additive is present in a coating on the capacitor negative electrode in an amount that increases the potential window of the capacitor negative electrode to at least −

1.2V.

12. The lead-acid battery of claim 9, wherein the total additive content is between 5-40 wt %, based on the total capacitor coating composition.

13. The lead-acid battery of claim 9, wherein the negative capacitor electrode additive comprises the compounds of the following metals in oxide, sulfate or hydroxide from:

between 1-40 wt % Pb,;

1-20 wt % Zn;

0-5 wt % Cd and 0-5 wt % Ag.

14. The lead-acid battery of claim 1, wherein the lead-acid battery comprises at least one capacitor positive electrode comprising:

a high surface area capacitor material, and a capacitor positive electrode additive comprising;

Pb₂O₃,

an oxide, hydroxide or sulfate of antimony, and

optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead.

15. The lead-acid battery of claim 14, wherein capacitor positive electrode additive is present in amount increases the potential window of the capacitor positive electrode to at least ±

1.2V.

16. The lead-acid battery of claim 14, wherein the capacitor positive electrode additive is present in an amount of 5-40 wt % based on the total capacitor positive electrode coating composition.

17. The lead-acid battery of claim 14, wherein the positive capacitor electrode additive comprises between 0-30 wt % Pb in oxide, sulfate or hydroxide form, 1-10 wt % Pb₂O₃, 0-2 wt % Fe in oxide, sulfate or hydroxide form and 0.05 to 1 wt % Sb in oxide, sulfate or hydroxide form.

18. The lead-acid battery of claim 1, wherein the lead-acid battery comprises a negative electrodes with at least two regions, including a battery-electrode material region and a capacitor-electrode material region.

19. The lead-acid battery of claim 18, wherein the negative electrode comprises a lead-based battery electrode material region on one face, and a capacitor negative electrode material region on the opposite face.

20. The lead-acid battery of claim 1, wherein the asymmetric capacitor part has ultracapacitor capacitance.

21. The lead-acid battery of claim 1, wherein the asymmetric capacitor part has supercapacitor capacitance.

22. The lead-acid battery of claim 1, wherein the electrolyte is sulphuric acid.

23. The lead-acid battery of claim 1, wherein each of the positive and negative electrodes is separated from adjacent electrodes by porous separators.

24. The lead-acid battery of claim 23, wherein the separators located between adjacent lead-based negative electrodes and lead dioxide-based positive electrodes have a thickness of between 1 and 2.5 millimetres.

25. The lead-acid battery of claim 23, wherein the separators located in contact with a capacitor electrode surface have a thickness of between 0.01 and 0.1.

37. The lead-acid battery of claim 1, wherein the lead-acid battery comprises a negative electrode with at least two regions, including a battery-electrode material region and a capacitor-electrode material region.

38. The lead-acid battery of claim 37, wherein the negative electrode comprises a lead-based battery electrode material region on one face, and a capacitor negative electrode material region on the opposite face.

26. A lead-acid battery comprising:

at least one lead-based negative electrode,

at least one lead dioxide-based positive electrode,

at least one capacitor negative electrode, and

electrolyte in contact with the electrodes,

wherein the positive electrode and the lead-based negative electrode define a battery part, and the positive electrode and the capacitor negative electrode define an asymmetric capacitor part, with the positive electrode shared by the battery part and the asymmetric capacitor part, and wherein the lead-based negative and capacitor negative electrodes are connected to a negative busbar, and the positive electrode or electrodes are connected to a positive busbar.

27. The lead-acid battery of claim 26, wherein the electrodes alternate between positive and negative electrodes.

28. The lead-acid battery of claim 26, wherein the capacitor electrode comprises a high surface area carbon material.

29. The lead-acid battery of claim 26, wherein the capacitor negative electrode comprises a high surface area active material and an additive or additive mixture comprising an oxide, hydroxide or sulfate of lead, zinc, cadmium, silver and bismuth, or a mixture thereof.

30. The lead-acid battery of claim 29, wherein the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.

31. The lead-acid battery of claim 29, wherein the additive is present in a coating on the capacitor negative electrode in an amount that increases the potential window of the capacitor negative electrode to at least −

1.2V.

32. The lead-acid battery of claim 29, wherein the total additive content is between 5-40 wt %, based on the total capacitor coating composition.

33. The lead-acid battery of claim 29, wherein the negative capacitor electrode additive comprises the compounds of the following metals in oxide, sulfate or hydroxide from:

between 1-40 wt % Pb;

1-20 wt % Zn;

0-5 wt % Cd and 0-5 wt % Ag.

34. The lead-acid battery of claim 26, wherein the lead-acid battery comprises at least one capacitor positive electrode comprising:

a high surface area capacitor material, and a capacitor positive electrode additive comprising;

Pb₂O₃,

an oxide, hydroxide or sulfate of antimony, and

optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead.

35. The lead-acid battery of claim 34, wherein the capacitor positive electrode additive is present in an amount of 5-40 wt %.

36. The lead-acid battery of claim 34, wherein the positive capacitor electrode additive comprises between 0-30 wt % Pb in oxide, sulfate or hydroxide form, 1-10 wt % Pb₂O₃, 0-2 wt % Fe in oxide, sulfate or hydroxide form and 0.05 to 1 wt % Sb in oxide, sulfate or hydroxide form.

39. The lead-acid battery of claim 26, wherein the asymmetric capacitor part has ultracapacitor capacitance.

40. The lead-acid battery of claim 26, wherein the asymmetric capacitor part has supercapacitor capacitance.

41. The lead-acid battery of claim 26, wherein the electrolyte is sulphuric acid.

42. The lead-acid battery of claim 26, wherein each of the positive and negative electrodes is separated from adjacent electrodes by porous separators.

43. The lead-acid battery of claim 42, wherein the separators located between adjacent lead-based negative electrodes and lead dioxide-based positive electrodes have a thickness of between 1 and 2.5 millimetres.

44. The lead-acid battery of claim 42, wherein the separators located in contact with a capacitor electrode surface have a thickness of between 0.01 and 0.1.

45. A lead-acid battery comprising an alternating series of positive and negative electrodes and an electrolyte in contact with the electrodes, wherein:

at least one pair of adjacent positive and negative electrode regions store energy capacitively, and

at least one pair of adjacent lead dioxide positive and lead negative battery electrode regions store energy electrochemically,

and wherein the positive electrodes are directly connected by a first conductor and the negative electrodes are directly connected by a second conductor.

46. The lead-acid battery of claim 45, wherein one of the positive and negative electrode regions is a capacitor electrode region.

47. The lead-acid battery of claim 46, wherein the capacitor electrode region comprises a high surface area carbon material.

48. The lead-acid battery of claim 47, wherein the capacitor electrode region is a negative capacitor electrode region, and comprises a high surface area carbon material and an additive or additive mixture comprising an oxide, hydroxide or sulfate of lead, zinc, cadmium, silver and bismuth, or a mixture thereof.

49. The lead-acid battery of claim 48, wherein the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.

50. The lead-acid battery of claim 48, wherein the total additive content is between 5-40 wt %.

51. The lead-acid battery of claim 47, wherein the negative capacitor electrode additive comprises compounds of the following metals in oxide, sulfate or hydroxide from:

between 1-40 wt % Pb;

1-20 wt % Zn;

0-5 wt % Cd and 0-5 wt % Ag.

52. The lead-acid battery of claim 47, wherein the capacitor electrode region is a positive capacitor electrode region, and comprises:

a high surface area capacitor material, and a capacitor positive electrode additive comprising;

Pb₂O₃,

an oxide, hydroxide or sulfate of antimony, and

optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead.

53. The lead-acid battery of claim 52, wherein the capacitor positive electrode additive is present in an amount of 5-40 wt %.

54. The lead-acid battery of claim 52, wherein the positive capacitor electrode additive comprises between 0-30 wt % Pb in oxide, sulfate or hydroxide form, 1-10 wt % Pb₂O₃, 0-2 wt % Fe in oxide, sulfate or hydroxide form and 0.05 to 1 wt % Sb in oxide, sulfate or hydroxide form.

55. The lead-acid battery of claim 45, wherein the lead negative battery region is on one face of a negative electrode, and a negative capacitor material region is on the opposite face of the negative electrode.

56. The lead-acid battery of claim 45, wherein the electrolyte is sulphuric acid.

57. The lead-acid battery of claim 45, wherein each of the positive and negative electrodes is separated from adjacent electrodes by porous separators.

58. The lead-acid battery of claim 57, wherein the separators located between adjacent lead-based negative electrode regions and lead dioxide-based positive electrode regions have a thickness of between 1 and 2.5 millimetres.

59. The lead-acid battery of claim 57, wherein the separators located in contact with a capacitor electrode region have a thickness of between 0.01 and 0.1.

60. A hybrid battery-apacitor comprising:

at least one battery-type positive electrode,

at least one battery-type negative electrode,

at least one capacitor-type electrode selected from a capacitor negative electrode and a capacitor positive electrode, wherein the capacitor negative electrode comprises a high surface area capacitor material and one or more additives selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth, and wherein the capacitor positive electrode comprises;

a high surface area capacitor material,

Pb₂O₃,

an oxide, hydroxide or sulfate of antimony, and

optionally one or more additives selected from oxides, hydroxides and sulfates of iron and lead, and

an electrolyte in contact with the electrodes,

wherein a battery part is formed between the battery-type positive electrode and the battery-type negative electrode, and an asymmetric capacitor part is formed between the capacitor electrode and one of the battery-type electrodes,

wherein one of the battery-type electrodes is shared by the battery part and the asymmetric capacitor part, and

wherein the negative electrodes are in direct electrical connection to a first conductor, and the positive electrodes are in direct electrical connection to a second conductor.

61. The hybrid battery-capacitor of claim 60, wherein the battery-type positive electrode comprises an electrode material selected from lead dioxide, nickel oxide, silver oxide, manganese oxide, lithium polymer materials, mixed lithium oxides including lithium nickel oxides, lithium cobalt oxides, lithium manganese oxides and lithium vanadium oxides, and lithium conductive polymer cathode materials.

62. The hybrid battery-capacitor of claim 60, wherein the battery-type negative electrode comprises an electrode material selected from lead, zinc, cadium, metal hydrides, lithium in metal or alloy form with other metals such as aluminium, and lithium ion intercalation materials.

63. The hybrid battery-capacitor of claim 60, wherein the electrodes alternate between positive and negative electrodes.

64. The hybrid battery-capacitor of claim 60, wherein the high surface area material is a high surface area carbon material.

65. The hybrid battery-capacitor of claim 60, wherein the capacitor-type electrode is a capacitor negative electrode, and the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.

66. The hybrid battery-capacitor of claim 65, wherein the additive is present in a coating on the capacitor negative electrode in an amount that increases the voltage window of the capacitor negative electrode to at least −

1.2V.

67. The hybrid battery-capacitor claim 65, wherein the total additive content is between 5-40 wt %, based on the total capacitor coating composition.

68. The hybrid battery-capacitor of claim 65, wherein the negative capacitor electrode additive comprises compounds of the following metals in oxide, sulfate or hydroxide from:

between 1-40 wt % Pb;

1-20 wt % Zn;

0-5 wt % Cd and 0-5 wt % Ag.

69. The hybrid battery-capacitor of claim 60, wherein the capacitor-type electrode is a capacitor positive electrode, and the capacitor positive electrode additive is present in an amount of 5-40 wt %.

70. The lead-acid battery of claim 69, wherein the positive capacitor electrode additive comprises between 0-30 wt % Pb in oxide, sulfate or hydroxide form, 1-10 wt % Pb₂O₃, 0-2 wt % Fe in oxide, sulfate or hydroxide form and 0.05 to 1 wt % Sb in oxide, sulfate or hydroxide form.

71. The hybrid battery-capacitor of claim 60, wherein the hybrid battery-capacitor comprises both a capacitor positive electrode and a capacitor negative electrode.

72. The hybrid battery-capacitor of claim 60, wherein each of the positive and negative electrodes is separated from adjacent electrodes by porous separators.

73. A capacitor negative electrode comprising a current collector and a paste coating, the paste coating comprising a high surface-area capacitor material, a binder and between 5-40 wt %, based on the weight the paste coating, of an additive or additive mixture selected from oxides, hydroxides or sulfates of lead, zinc, cadmium, silver and bismuth, with the proviso that the additive includes at least one oxide, hydroxide or sulfate of lead or zinc.

75. An asymmetric capacitor comprising a capacitor negative electrode according to claim 73, or a capacitor positive electrode as defined above, a battery-type electrode chose from lead or lead dioxide electrode, and an electrolyte.

74. A capacitor positive electrode comprises a current collector and a paste coating, the paste coating comprising a high surface area capacitor material, a binder and between 10-40 wt %, based on the weight the paste coating, of an additive mixture comprising:

Pb₂O₃,

an oxide, hydroxide or sulfate of antimony, and

optionally one or more oxides, hydroxides or sulfates of iron and lead.