Electrodies containing a conductive metal oxide

• US 5,045,170 A
• Filed: 05/02/1989
• Issued: 09/03/1991
• Est. Priority Date: 05/02/1989
• Status: Expired due to Fees

• Current Assignee: Johnson Controls Technology Company (Johnson Controls International plc)
• Original Assignee: Globe-Union Inc.
• Inventors: Kao, Wen-Hong, Bullock, Norma K.
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US07/345,993
• Time in Patent Office: 854 Days
• Field of Search: 429/232, 429/245, 429/227, 429/225, 429/210, 429/228, 429/238, 204/290 F, 204/96, 204/280, 252/182.1
• US Class Current: 204/280
• CPC Class Codes: C25B 1/13 Ozone
• CPC Class Codes: C25B 1/21 Manganese oxides
• CPC Class Codes: C25B 11/0773 of the perovskite type
• CPC Class Codes: H01B 1/02 mainly consisting of metals or alloys
• CPC Class Codes: H01B 1/08 oxides
• CPC Class Codes: H01G 11/30 characterised by their material
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01M 4/20 of pasted electrodes
• CPC Class Codes: H01M 4/624 Electric conductive fillers
• CPC Class Codes: H01M 4/68 for use in lead-acid accumulators
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

An electrode suitable for use as a lead-acid battery plate contains an inorganic metal oxide additive which enhances the formation of the plate. The additive is electrically conductive, stable in aqueous solutions of sulfuric acid, but does not participate in the electrode reaction. Suitable metal oxides include barium metaplumbate and other ceramic perovskite materials having similar properties. The conductive ceramic may also be used in electrodes for bipolar lead-acid batteries and in an electrode, particularly an anode (positive electrode), used in electrolytic processes.

Claims

1. In an electrode configured for use in a lead-sulfuric acid battery, including a conductive current collector and a layer of an active lead material in contact with said collector, the improvement which comprises an electrically conductive, sulfuric acid-resistant metal oxide of perovskite structure in contact with said layer, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

2. The electrode of claim 1, wherein said conductive metal oxide has an oxygen overpotential about the same as or greater than PbO₂ when employed under like conditions in a positive electrode of a lead-sulfuric acid battery.

3. The electrode of claim 1, wherein said conductive metal oxide has a hydrogen overpotential about the same as or greater than Pb when employed under like conditions in a negative electrode of a lead-sulfuric acid battery.

4. The electrode of claim 1, wherein said metal oxide is coated on said current collector.

5. The electrode of claim 4, wherein said metal oxide is coated on said current collector between said current collector and said layer of active lead material.

6. The electrode of claim 5, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

7. The electrode of claim 1, wherein said current collector consists essentially of lead.

8. In an electrode including a conductive current collector and an active lead material in contact with said collector, the improvement wherein said active material contains an electrically conductive, sulfuric acid-resistant metal oxide material which consists essentially of a compound of the formula A_a B_b O_c, wherein A is Sr, Ba, Zn, Cd, or Ra, B is Zr, Sn, or Pb, 0.5≦

a≦

1, 0.5≦

b≦

1, and 2≦

c≦

3.

9. The electrode of claim 8, wherein said active lead material contains about 0.1 to 50 wt. % of said metal oxide.

10. The electrode of claim 8, wherein said electrode is a positive electrode in which said collector consists essentially of lead, and said active lead material comprises a lead sulfate compound which is converted to lead dioxide when said electrode is charged in a lead-sulfuric acid battery.

11. The electrode of claim 10, wherein said collector comprises a generally flat grid, and said active lead material forms a layer on said grid.

12. The electrode of claim 10, wherein said collector comprises an elongated rod, said electrode further comprises a sheath made of a sulfuric acid-resistant fiber mesh, and said active lead material is disposed between said collector and said sheath.

13. The electrode of claim 8, wherein said conductive metal oxide is selected from the group consisting of ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, CdPb₀.5 O₂, Cd₀.5 PbO₂.5, and combinations thereof.

14. The electrode of claim 8, further comprising a layer consisting essentially of said metal oxide compound interposed between said collector and said active lead material.

15. The electrode of claim 8, wherein said conductive metal oxide has an oxygen overpotential about the same as or greater than PbO₂ when employed under like conditions in a positive electrode of a lead-sulfuric acid battery wherein the aqueous sulfuric acid electrolyte has a specific gravity in the range of about 1.001 to 1.4 and at a temperature in the range of about -40°

to 80°

C., and has a hydrogen overpotential about the same or as greater than Pb when employed under like conditions in a negative electrode of a lead-sulfuric acid battery wherein the aqueous sulfuric acid electrolyte has a specific gravity in the range of 1.001 to 1.4 and at a temperature in the range of about -40°

to 80°

C.

16. The electrode of claim 8, wherein A is Ba.

17. The electrode of claim 8, wherein said compound is barium metaplumbate.

18. The electrode of claim 17, wherein said active lead material contains from about 0.1 to 8 wt. % of barium metaplumbate.

19. In a lead-acid battery including a casing, positive and negative electrodes disposed in said casing, a separator interposed between said electrodes, and a sulfuric acid electrolyte in contact with said electrodes and separator, the improvement comprising:

one of said electrodes comprises a current collector, a layer of an active lead material in contact with said collector, and an electrically conductive, sulfuric acid-resistant metal oxide of perovskite structure in contact with said layer, wherein said metal oxide consists essentially of a compound of the formula A_a B_b O_c, wherein A is Sr, Ba, Zn, Cd, or Ra, B is Zr, Sn, or Pb, 0.5<

a<

1, 0.5<

b<

1, and 2<

c<

3.

20. The battery of claim 19, wherein said current collector comprises a grid consisting essentially of lead, and said active lead material comprises a layer deposited on said grid and contains lead sulfate which is converted to lead dioxide when said electrode is charged in a lead-sulfuric acid battery.

21. The battery of claim 19, wherein said compound is barium metaplumbate.

22. The battery of claim 21, wherein said active lead material contains from about 0.1 to 8 wt. % of barium metaplumbate.

23. The battery of claim 19, wherein the improvement further comprises said negative electrode contains carbon therein.

24. The battery of claim 19, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

25. The battery of claim 19, wherein said current collector is a grid consisting essentially of lead.

26. A paste mixture, comprising particles of a lead oxide compound, a lead sulfate compound, and a conductive, sulfuric acid-resistant metal oxide of perovskite structure, said particles being dispersed in an amount of water effective to form a paste, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

27. The paste mixture of claim 26, wherein said lead oxide compound is selected from the group consisting of PbO, Pb₃ O₄, and mixtures thereof, said lead sulfate compound is selected from the group consisting of PbSO₄, PbO.PbSO₄, 3PbO.PbSO₄.H₂ O, 4PbO.PbSO₄, and mixtures thereof, and said metal oxide is BaPbO₃.

28. The paste mixture of claim 27, wherein solids in said paste consist essentially of 0.01 to 50 wt. % of BaPbO₃, up to about 0.5 wt. % of a fiber, and the balance is said lead oxide compound and said lead sulfate compound, and the amount of water in said paste is in the range of about 0.15 to 0.2 ml/gm of said solids.

29. In a method for the electrolytic synthesis of a product from a reactant in an aqueous reaction medium, including the step of applying an electrical current to said medium by means of electrodes including an anode and a cathode immersed therein to form said product, the improvement comprising:

at least one of said electrodes contains a conductive, sulfuric-acid resistant metal oxide of perovskite structure which remains unreactive during said electrolytic synthesis, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

30. The method of claim 29, wherein said compound consisting essentially of barium metaplumbate, and said medium is aqueous sulfuric acid.

31. The method of claim 29, wherein said reactant comprises MnSO₄, and said product comprises MnO₂.

32. The method of claim 29, wherein said reactant comprises water, and said product comprises ozone and hydrogen.

33. In a bipolar electrode for use in a lead-acid bipolar battery, including a conductive substrate having a pair of layers of positive and negative active material disposed on opposite sides thereof, the improvement wherein said substrate comprises:

particles of a conductive metal oxide which is substantially stable in aqueous sulfuric acid and consists essentially of a compound having the formula A_a B_b O_c, wherein A is Sr, Ba, Zn, Cd, or Ra, B is Zr, Sn, or Pb, 0.5≦

a≦

1, 0.5≦

b≦

1, and 2≦

c≦

3; and

a substantially sulfuric acid-resistant binder in which said conductive particles are dispersed.

34. The bipolar electrode of claim 33, wherein said conductive metal oxide consists essentially of barium metaplumbate.

35. The bipolar electrode of claim 33, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

36. The bipolar electrode of claim 35, wherein said binder is olyethylene.

37. In a bipolar battery including a casing, a plurality of bipolar electrodes disposed in said casing each including a conductive substrate having a pair of layers of positive and negative active material disposed on opposite faces thereof, at least one separator interposed between said bipolar electrodes, and an electrolyte in which said electrodes and separator are in contact, the improvement wherein said substrate comprises:

particles of a conductive, sulfuric acid-resistant metal oxide which is substantially stable in aqueous sulfuric acid and consists essentially of a compound having the formula A_a B_b O_c, wherein A is Sr, Ba, Zn, Cd, or Ra, B is Zr, Sn, or Pb, 0.5≦

a≦

1, 0.5≦

b≦

1, and 2≦

c≦

3; and

a sulfuric acid-resistant binder in which said conductive particles are dispersed.

38. The bipolar battery of claim 37, wherein said compound is barium metaplumbate.

39. A battery component for use in a lead-sulfuric acid battery in contact with a sulfuric acid electrolyte, wherein said component is coated with a thin layer of a conductive, sulfuric acid-resistant metal oxide of perovskite structure, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

40. The battery component of claim 39, wherein said component is a battery post.

41. The battery component of claim 39, wherein said component is an intercell connector.

42. The battery component of claim 39, wherein said component is a strap.

43. The battery component of claim 39, wherein said component is an end plate.

44. The battery component of claim 39, wherein said metal oxide layer is formed by deposition.

45. The battery component of claim 39, wherein said metal oxide layer is formed by applying a paint to said component, which paint comprises particles of said metal oxide in a binder.

46. The battery component of claim 39, wherein said compound is barium metaplumbate.

47. An electrode for use in the electrolytic synthesis of a product from a reactant in an aqueous sulfuric acid reaction medium, comprising a conductive, sulfuric acid-resistant metal oxide of perovskite structure, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

48. The electrode of claim 47, wherein said electrode comprises a conductive substrate and a coating of said metal oxide deposited on said substrate.

49. The electrode of claim 48, wherein said metal oxide is sintered to form said conductive substrate.

50. The electrode of claim 48, wherein said conductive substrate comprises said metal oxide embedded in an inert, plastic binder.

51. The electrode of claim 47, wherein said compound consists essentially of barium metaplumbate.

52. In an apparatus for the electrolytic synthesis of a product from a reactant in an aqueous sulfuric acid reaction medium, including a container for said medium, a pair of electrodes including an anode and a cathode disposable in said medium, and means for applying an electrical current to said medium through said electrodes to form said compound, the improvement wherein one of said electrodes contains a conductive, sulfuric acid-resistant metal oxide of perovskite structure which remains substantially unreactive during said electrolytic synthesis, wherein said metal oxide consists essentially of a compound selected from the group consisting of BaPbO₃, ZnSnO₃, CdSnO₃, ZnPbO₃, CdPbO₃, Cd₂ PbO₄, and CdPb₂ O₅, and combinations thereof.

53. The apparatus of claim 52, wherein said compound consists essentially of barium metaplumbate.

54. The apparatus of claim 53, wherein said one electrode comprises a conductive substrate and a coating of said metal oxide deposited on said substrate.

55. The apparatus of claim 54, wherein said metal oxide is sintered to form said conductive substrate.

56. The apparatus of claim 54, wherein said conductive substrate comprises said metal oxide embedded in an inert, plastic binder.

57. The apparatus of claim 52, wherein said one electrode is said anode, and said cathode comprises a material selected from lead, lead oxide, carbon, and a noble metal.