Photoelectrochemical cells having functions as a solar cell and a secondary cell

• US 4,916,035 A
• Filed: 08/08/1988
• Issued: 04/10/1990
• Est. Priority Date: 08/06/1987
• Status: Expired due to Term

• Current Assignee: Matsushita Electric Industrial Company Limited 1006 OAZA Kadoma-Shi Osaka Japan
• Original Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Inventors: Takeda, Takeshi, Yamashita, Akio, Sekido, Satoshi, Tsuchiya, Sohji
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US07/232,637
• Time in Patent Office: 610 Days
• Field of Search: 429/111
• US Class Current: 429/111
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01M 10/0562 Solid materials
• CPC Class Codes: H01M 10/465 with solar battery as charging system
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: H01M 4/52 of nickel, cobalt or iron
• CPC Class Codes: H01M 4/581 Chalcogenides or intercalation compounds thereof
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Photoelectrochemical cells comprising a positive electrode comprised of an n-type conductive semiconductor and a compound capable of reversibly intercalating or deintercalating metal atoms or ions, an ion conductive solid electrolyte layer, a negative electrode, and current collectors for the positive and negative electrodes. The intercalating or deintercalating compound is a Chevrel compound or vornite. The photoelectrochemical cell serves as both solar and secondary cells. Various cell constructions are also described including a multi-layered structure and a two-cell construction.

Claims

1. A photoelectrochemical cell comprising:

a positive electrode made of a conductive semiconductor which is able to generate electron-hole pairs when irradiated with light and a Chevrel compound having a three-dimensional structure which allows metal atoms thereof to be deintercalated in the form of metal ions by reaction with said holes;

a current collector for said positive electrode provided in contact with said positive electrode;

a metal ion conductive solid electrolyte layer provided in contact with one side of said positive electrode to receive said metal ions when said Chevrel compound is deintercalated;

a negative electrode provided in contact with said solid electrolyte layer without direct contact with said positive electrode; and

a current collector for said negative electrode provided in contact with said negative electrode, whereby when light is irradiated on said positive electrode so that said conductive semiconductor adsorbs light at an energy level higher than a band gap thereof, said cell is photoelectrochemically charged and is discharged when said positive and negative electrodes are electrically connected.

2. A photoelectrochemical cell according to claim 1, wherein said conductive semiconductor comprises an n-type semiconductor selected from the group consisting of ZrS₂, ZrS₃, TiS₂, HfS₂, HfSe₂, SnS₂, MoS₂, InSe, Si, Ge, TiO₂, GaAs, CdS, ZnO, and mixtures thereof.

3. A photoelectrochemical cell according to claim 1, wherein said conductive semiconductor comprises an n-type semiconductive layer compound having a hexagonal or rhombohedral crystal form and selected from the group consisting of ZrS₂, ZrS₃, TiS₂, HfS₂, HfSe₂, SnS₂, MoS₂, InSe, and mixtures thereof.

4. A photoelectrochemical cell according to claim 1, wherein said metal atom-containing compound comprises a Chevrel compound of the formula, Cu_x Mo₆ S_8-y or Ag_x Mo₆ S_8-y in which x is 0<

x≦

4 and y is from 0 to 0.4.

5. A photoelectrochemical cell according to claim 4, wherein said Chevrel compound comprises Cu₂ Mo₆ S₈.

6. A photoelectrochemical cell according to claim 4, wherein said Chevrel compound comprises Cu_x Mo₆ S_8-y in which x is 0<

x≦

4 and y is from 0.1 to 0.4.

7. A photoelectrochemical cell according to claim 1, wherein said positive electrode includes one layer made of a mixture of said conductive semiconductor and said Chevrel compound.

8. A photoelectrochemical cell according to claim 1, wherein said positive electrode includes a two-layered construction having a photo-electrode comprising said conductive semiconductor and a capacitive electrode comprising said Chevrel compound, said photo-electrode being directly exposed to light.

9. A photoelectrochemical cell according to claim 8, wherein said photo-electrode comprises an n-type semiconductor of the formula, (Ti_a Zr_1-a)S_2-y, in which 0.5≦

a≦

0.75 and b≧

0.1.

10. A photoelectrochemical cell according to claim 8, wherein said photo-electrode has a thickness sufficient to absorb substantially all light incident thereon.

11. A photoelectrochemical cell according to claim 8, wherein said capacitive electrode comprises a Chevrel compound of the formula, Cu_x Mo₆ S_8-y or Ag_x Mo₆ S_8-y in which x is 0<

x≦

4 and y is from 0 to 0.4.

12. A photoelectrochemical cell according to claim 11, wherein said Chevrel compound comprises Cu₂ Mo₆ S₈.

13. A photoelectrochemical cell according to claim 11, wherein said Chevrel compound comprises Cu_x Mo₆ S_y in which x is 0<

x≦

4.0 and y is from 0.1 to 0.4.

14. A photoelectrochemical cell according to claim 1, wherein said metal ion conductive solid electrolyte layer comprises a Cu ion conductive solid electrolyte.

15. A photoelectrochemical cell according to claim 14, wherein said Cu⁺ ion conductive solid electrolyte is of the formula, Rb_h K_1-h Cu₄ X, in which h is from 0.8 to 1, and X is a halogen or a mixture of halogens.

16. A photoelectrochemical cell according to claim 15, wherein the formula is Rb_h K_1-h Cu₄ I₁.5 Cl₃.5 in which h is from 0.8 to 1.

17. A photoelectrochemical cell according to claim 16, wherein the formula is RbCu₄ I₁.5 Cl₃.5.

18. A photoelectrochemical cell according to claim 14, wherein said Cu ion conductive solid electrolyte comprises a member selected from the group consisting of RbAg₄ I₅, RbCu₄ I₁.5 Cl₃.5, Rb₄ 4.2Cu₁₅.8 I₆.8 Cl₁₃.2, Rb₄.2 Cu₁₅.8 I₇.0 Cl₁₃.0, Rb₄.2 Cu₁₅.8 I₇.2 C₁₂.8, Rb₄.2 Cu₁₅.8 I₇.4 C₁₂.6, Rb₃.8 Cu₁₆.2 I₆.8 C₁₃.2, Rb₃.8 Cu₁₆.2 I₇.0 C₁₃.0, Rb₃.8 Cu₁₆.2 I₇.2 C₁₂.8, Rb₃.8 Cu₁₆.2 I₇.4 C₁₂.6, Rb₄.0 Cu₁₆ I₆.6 C₁₃.4, Rb₄.0 Cu₁₆ I₆.8 C₁₃.2, Rb₄.0 Cu₁₆ I₇.0 C₁₃.0, Rb₄.0 Cu₁₆ I₇.2 C₁₂.8, Rb₄.0 Cu₁₆ I₇.4 C₁₂.6, Rb₄.0 Cu₁₆ I₇.6 C₁₂.4, Rb₄.0 Cu₁₆ I₇.8 C₁₂.2, Rb₄.0 Cu₁₆ I₈.0 C₁₂.0, and mixtures thereof.

19. A photoelectrochemical cell according to claim 1, wherein said negative electrode comprises a mixture of a Cu⁺ ion conductive solid electrolyte, electrolytic copper powder, and Cu₂ S.

20. A photoelectrochemical cell according to claim 1, wherein said negative electrode comprises Ag or Cu.

21. A photoelectrochemical cell according to claim 1, wherein said positive electrode, said solid electrolyte layer, and said negative electrode are disposed in this order.

22. A photoelectrochemical cell according to claim 1, wherein said positive electrode and said negative electrode are disposed on one surface of said solid electrolyte layer in side-by-side, spaced apart relation so that there is no direct contact therebetween.

23. A photoelectrochemical cell according to claim 1, further comprising a body of a transparent substrate material, and said positive electrode, said solid electrolyte layer and said negative electrode being disposed on one surface of said body in this order.

24. A photoelectrochemical cell according to claim 1, further comprising a body of a transparent substrate material, and said positive electrode, said solid electrolyte layer and said negative electrode being disposed on one surface of said body in such a way that said positive electrode and said negative electrode are in side-by-side spaced part relation, on one side thereof and said solid electrolyte layer is disposed on another side of said positive and negative electrodes.

25. A photoelectrochemical cell according to claim 1, wherein said negative electrode comprises a two-layered construction including a photo-electrode and a capacitive electrode.

26. A photoelectrochemical cell according to claim 25, wherein said photo-electrode comprises a p-type semiconductor selected from the group consisting of FePS₃, Cu₃ PS₄, Cu_6-c PS₅ I in which 0<

c<

1, polyacetylene, Si, Ge, GaAs, SiC, CdS, PbO, CdTe, and mixtures thereof.

27. A photoelectrochemical cell according to claim 25, wherein said capacitive electrode comprises a Chevrel compound.

28. A photoelectrochemical cell according to claim 27, wherein said capacitive electrode comprises said Chevrel compound to which a Cu⁺ ion conductive solid electrolyte is added.

29. A photoelectrochemical cell according to claim 28, wherein said solid electrolyte is of the formula, Rb_h K_1-h Cu₄ X, in which h is from 0.8 to 1, and X is a halogen or a mixture of halogens.

30. A photoelectrochemical cell according to claim 29, wherein the formula is Rb_h K_1-h Cu₄ I₁.5 Cl₃.5 in which h is from 0.8 to 1.

31. A photoelectrochemical cell according to claim 29, wherein the formula is RbCu₄ I₁.5 Cl₃.5.

32. A photoelectrochemical cell according to claim 28, wherein said Cu ion conductive solid electrolyte is a member selected from the group consisting of RbAg₄ I₅, RbCu₄ I₁.5 Cl₃.5, Rb₄.2 Cu₁₅.8 I₆.8 Cl₁₃.2, Rb₄.2 Cu₁₅.8 I₇.0 Cl₁₃.0, Rb₄.2 Cu₁₅.8 I₇.2 C₁₂.8, Rb₄.2 Cu₁₅.8 I₇.4 C₁₂.6, Rb₃.8 Cu₁₆.2 I₆.8 C₁₃.2, Rb₃.8 Cu₁₆.2 I₇.0 C₁₃.0, Rb₃.8 Cu₁₆.2 I₇.2 C₁₂.8, Rb₃.8 Cu₁₆.2 I₇.4 C₁₂.6, Rb₄.0 Cu₁₆ I₆.6 C₁₃.4, Rb₄.0 Cu₁₆ I₆.8 C₁₃.2, Rb₄.0 Cu₁₆ I₇.0 C₁₃.0, Rb₄.0 Cu₁₆ I₇.2 C₁₂.8, Rb₄.0 Cu₁₆ I₇.4 C₁₂.6, Rb₄.0 Cu₁₆ I₇.6 C₁₂.4, Rb₄.0 Cu₁₆ I₇.8 C₁₂.2, Rb₄.0 Cu₁₆ I₈.0 C₁₂.0, and mixtures thereof.

33. A photoelectrochemical cell according to claim 1, wherein said positive electrode comprises a photo-electrode and a capacitive electrode and said solid electrolyte layer comprises a molded layer of a Cu⁺ ion conductive solid electrolyte, in which said photo-electrode comprises a molded mixture of an n-type semiconductive layer compound and said Cu⁺ ion conductive solid electrolyte, said capacitive electrode comprises a molded mixture of a copper Chevrel compound and said Cu⁺ ion conductive solid electrolyte, said negative electrode comprises a molded mixture of electrolytic copper powder, Cu₂ S and said Cu⁺ ion conductive solid electrolyte, said current collector for said negative electrode comprises copper, and said current collector for said positive electrode comprises graphite.

34. A photoelectrochemical cell according to claim 1, wherein said positive electrode comprises a photo-electrode and a capactive electrode superposed on one side of said photo-electrode, the current collector for the positive electrode being disposed on another side of said photo-electrode, and said solid electrolyte layer, said negative electrode and said current collector superposed on said capacitive electrode in this order.

35. A photoelectrochemical cell according to claim 1, wherein said photoelectrochemical cell comprises a thin film construction which comprises, disposed in the following order, a Cu film current collector for said negative electrode, a film comprising a mixture of copper and Cu₂ S as said negative electrode, a Cu⁺ ion conductive solid electrolyte film as said solid electrolyte, said positive electrode comprises a film of Cu_x Mo₆ S_8-y in which x is 0<

x≦

4 and y is from 0 to 0.4 as a capacitive electrode and an n-type semiconductor layer compound film as a photo-electrode, and a graphite layer formed in contact with said photo-electrode for use as said current collector for said positive electrode.

36. A photoelectrochemical cell comprising a positive electrode including a photo-electrode comprised of (Ti_a Zr_1-a)S_2-b in which 0.5≦

a≦

0.75 and b≧

0.1 and a capacitive electrode comprised of a Cu_x Mo₆ S_8-y, in which 0<

x≦

4 and y is from 0 to 0.4 and formed on one side of said photo-electrode, a current collector for said positive electrode formed on another side of said photo-electrode in a manner not impeding passage of light into said photo-electrode from another side, a Cu⁺ ion conductive solid electrolyte layer, a copper-containing negative electrode, and a current collector for said negative electrode, said positive electrode, said solid electrolyte layer, said negative electrode and said current collector for said negative electrode being superposed in this order.

37. A photoelectrochemical cell according to claim 36, wherein said photo-electrode comprises a molded layer of a mixture of said Cu⁺ ion conductive solid electrolyte and (Ti_a Zr_1-a)S_2-b in which 0.5≦

a≦

0.75 and b≧

0.1, said capacitive electrode comprising a molded layer of a mixture of said Cu⁺ ion conductive solid electrolyte and Cu_x Mo₆ S_8-y in which 0≦

x≦

4 and y is from 0 to 0.4, said negative electrode comprises a molded layer of a mixture of said Cu⁺ ion conductive solid electrolyte, electrolytic copper powder and Cu_S, said current collector for said negative electrode comprises copper, and said current collector for said positive electrode comprises graphite.

38. A photoelectrochemical cell according to claim 36, wherein said photo-electrode comprises a film (Ti_a Zr_1-a)S_2-b in which 0.5≦

a≦

0.75 and b≧

0.1, said capacitive electrode comprises a film of Cu_x Mo₆ S_8-y in which 0<

x≦

4 and y is from 0 to 0.4, said negative electrode comprises a film of a mixture of electrolytic copper powder and Cu₂ S, said current collector for said negative electrode comprises a film of copper, and said current collector for said positive electrode comprises a film of graphite provided in contact with said photo-electrode.

39. A photoelectrochemical cell according to claim 38, further comprising an optically transparent substrate provided on said photo-electrode and a resin cover for protecting said photoelectrochemical cell.

40. A photoelectrochemical cell comprising an optically transparent substrate, a positive electrode which comprises an n-type semiconductor and a Chevrel compound, a negative electrode which comprises a p-type semiconductor and a Chevrel compound formed on one side of said substrate in side-by-side, spaced apart relation, a common metal ion conductive solid electrolyte layer provided in contact with both said positive and said negative electrode, and optically transparent current collectors for said positive and negative electrodes provided between said substrate and said positive and negative electrodes, respectively.

41. A photoelectrochemical cell according to claim 40, wherein said n-type semiconductor comprises at least one member selected from the group consisting of ZrS₂, ZrS₃, TiS₂, HfS₂, HfSe₂, SnS₂, MoS₂, InSe, Si, Ge, TiO₂, GaAs, CdS, ZnO, and mixtures thereof, and said p-type semiconductor comprises at least one member selected from the group consisting of FePS₃, Cu₃ PS₄, Cu_6-c PS₅ I in which 0<

c<

1, polyacetylene, Si, Ge, GaAs, SiC, CdS, PbO, and CdTe.

42. A photoelectrochemical cell according to claim 40, wherein said positive electrode includes a photo-electrode which comprises said n-type semiconductor and a capacitive electrode which comprises said Chevrel compound, and said negative electrode includes a photo-electrode which comprises said p-type semiconductor and a capacitive electrode which comprises said Chevrel compound, said photo-electrodes of said positive electrode and said negative electrode contacting with said respective current collectors, said capacitive electrodes contacting with said common solid electrolyte layer.

43. A photoelectrochemical cell according to claim 40, wherein said positive electrode comprises a film of a mixture of said n-type semiconductor and said Chevrel compound, and said negative electrode comprises a film of a mixture of said p-type semiconductor and said Chevrel compound.

44. A photoelectrochemical cell comprising:

an optically transparent substrate;

a positive electrode which includes a photo-electrode comprising a mixture of an n-type semiconductor capable of generating electron-hole pairs by irradiation of light and a Cu⁺ ion conductive solid electrolyte and a capacitive electrode provided in contact with said photo-electrode and comprising a mixture of a Chevrel compound having a three dimensional structure which allows metal atoms thereof to be deintercalated in the form of metal ions by reaction with said holes and said Cu⁺ ion conductive solid electrolyte;

a negative electrode which includes another photo-electrode comprising a mixture of a p-type semiconductor and said Cu⁺ ion conductive solid electrolyte and a capacitive electrode provided in contact with said another photo-electrode and comprising a mixture of either said Chevrel compound used in said positive electrode and said Cu⁺ ion conductive solid electrolyte, or Cu, CuS₂ and said Cu⁺ ion conductive solid electrolyte, said positive electrode and said negative electrode being spaced apart from each other and disposed on said substrate such that said photo-electrodes of said positive and negative electrodes are in contact with said substrate;

a common layer of said Cu⁺ ion conductive solid electrolyte in contact with said capacitive electrodes of said positive and negative electrodes; and

current collectors provided in contact with said respective photo-electrodes while permitting light to be passed into said respective photo-electrodes when the light is applied through said substrate.

45. A photoelectrochemical cell comprising:

an optionally transparent substrate;

a positive electrode which includes a photo-electrode comprising an n-type semiconductor and a capacitive electrode provided in contact with said photo-electrode and comprising a compound of the formula, Cu_x Mo₆ S_8-y wherein x=2.3 when y=0, x=1.9 when y=0.1 or x=1.2 when 0.2≦

y≦

0.4;

a negative electrode which includes another photo-electrode comprising a p-type semiconductor and a capacitive electrode provided in contact with said another photo-electrode and comprising a compound of the formula, Cu_x Mo₆ S_8-y wherein x=2.3 when y=0, x=1.9 when y=0.1 or x=1.1 when 0.2≦

y≦

0.4, or a mixture of Cu and Cu₂ S, said positive electrode and said negative electrode being spaced apart from each other and disposed on said substrate such that said photo-electrodes of said positive and negative electrodes are in contact with said substrate;

a common layer of a Cu⁺ ion conductive solid electrolyte in contact with said capacitive electrodes of said positive and negative electrodes; and

current collectors provided in contact with said respective photo-electrodes while permitting light to be passed into said respective photo-electrodes when the light is applied through said substrate.

46. A photoelectrochemical cell comprising;

an optically transparent substrate;

a positive electrode which includes a photo-electrode comprising an n-type semiconductor and a capacitive electrode provided in contact with said photo-electrode and comprising a compound of the formula, Cu_d Ti₆ S_2-e wherein d is from 0 to 0.22 and e is from 0 to 0.17;

a negative electrode which includes another photo-electrode comprising a p-type semiconductor and a capacitive electrode provided in contact with said another photo-electrode and comprising a compound of the formula, Cu_x Mo₆ S_8-y wherein x=2.3 when y=0, x=1.9 when y=0.1 or x=1.2 when 0.2≦

y≦

0.4, or a mixture of Cu and Cu₂ S, said positive electrode and said negative electrode being spaced apart from each other and disposed on said substrate such that said photo-electrodes of said positive and negative electrodes are in contact with said substrate;

a common layer of a Cu⁺ ion conductive solid electrolyte in contact with said capacitive electrodes of said positive and negative electrodes; and

current collectors provided in contact with said respective photo-electrodes while permitting light to be passed into said respective photo-electrodes when the light is applied through said substrate.

47. A photoelectrochemical cell comprising:

a positive electrode which includes a photo-electrode comprising an n-type semiconductor capable of generating electron-hole pairs when irradiated with light and a capacitive electrode comprising a Chevrel compound having a three-dimensional structure which allows metal atoms thereof to be deintercalated in the form of metal ions by reaction with said holes and contacting at least a part of said photo-electrode and having a current collector;

a negative electrode which includes another photo-electrode comprising a p-type semiconductor and a capacitive electrode comprising a Chevrel compound capable of reversibly intercalating and deintercalating metal atoms therein, in contact with at least a part of said another photo-electrode and having a current collector, said negative electrode being spaced apart from said positive electrode;

a common layer of a metal ion conductive solid electrolyte in contact with said capacitive electrodes; and

conductive electrodes contacting at least a part of said respective photo-electrodes for electrical connection of said photo-electrodes.

48. A photoelectrochemical cell according to claim 47, wherein said n-type semiconductor comprises at least one member selected from the group consisting of Si, Ge, CdS, TiO₂, GaAs, ZnO, ZrS₂, TiS₂, HfS₂, HfSe₂, SnS₂, MoS₂, and InSe, and said p-type semiconductor comprises at least one member selected from the group consisting of Si, Ge, GaAs, SiC, CdS, PbO, CdTe, FePS₃, Cu₃ PS₄, Cu_6-c PS₅ I in which 0<

c<

1, and polyacetylene.

49. A photoelectrochemical cell according to claim 47, wherein the same metal containing compound is used for both capacitive electrodes and comprises a member selected from group consisting of Chevrel compounds and vornites.

50. A photoelectrochemical cell according to claim 47, wherein said solid electrolyte comprises a Cu or Ag ion conductive solid electrolyte.

51. A photoelectrochemical cell according to claim 47, wherein said metal ion conductive solid electrolyte comprises a Cu⁺ ion conductive solid electrolyte, both photo-electrodes and both capacitive electrodes further comprise said Cu⁺ ion conductive solid electrolyte said current collectors for said capacitive electrodes comprise graphite, and said conductive electrodes comprise a light-permeable material.

52. A photoelectrochemical cell according to claim 51, wherein said conductive electrodes have such a shape as to permit light to pass into said respective photo-electrode.

53. A photoelectrochemical cell according to claim 47, wherein said photo-electrodes, said capacitive electrodes, said solid electrolyte layer and said conductive electrodes are each formed as thin films.

54. A photoelectrochemical cell which comprises:

an optically transparent substrate;

a first cell unit which is formed on one surface of said substrate and which includes an n-type photo-electrode comprising a mixture of an n-type semiconductor and a copper ion conductive solid electrolyte, a capacitive electrode formed on said n-type photo-electrode on one side thereof comprising a mixture of a compound of the formula, Cu_x Mo₆ S_8-y wherein 0<

x≦

4 and y is from 0.1 to 0.4 and said copper ion conductive solid electrolyte used in said n-type photo-electrode, a layer of said copper ion conductive solid electrolyte formed on another side of said capacitive electrode, a reversibly copper transferable electrode formed on said solid electrolyte layer and comprising a mixture of electrolytic copper powder, Cu₂ S and said copper ion conductive solid electrolyte, a first current collector formed on said reversibly copper transferable electrode, and a second current collector having an opening receiving said n-type photo-electrode therein and provided in contact with said capacitive electrode;

a second unit cell which is formed on said one surface of said substrate and which includes a p-type photo-electrode comprising a mixture of a p-type semiconductor and said copper ion conductive solid electrolyte, a capacitive electrode formed on said p-type photo-electrode on one side thereof and comprising a mixture of a compound of the formula, Cu_x Mo₆ S_8-y in which 0<

x≦

4 and y is from 0.1 to 0.4 and said copper ion conductive solid electrolyte, a layer of said copper ion conductive solid electrolyte formed on another side of said capacitive electrode, a reversibly copper transferable electrode formed on said solid electrolyte layer and comprising a mixture of electrolytic copper powder, Cu₂ S and said copper ion conductive solid electrolyte, a third current collector formed on said reversibly copper transferable electrode, and a fourth current collector having an opening receiving said p-type photo-electrode therein and provided in contact with said capacitive electrode, said first and second cell units being separated for each other; and

a conductive wire connecting said first and second cell units through said first and third current collectors.

55. A photoelectrochemical cell according to claim 54, wherein said n-type semiconductor comprises at least one member selected from the group consisting of n-TiO₂, n-CdS, n-InSe, n-ZrS₃, and n-ZrS₂, and said p-type semiconductor comprises at least one member selected from the group consisting of p-GaP, p-InSe, p-Cu_6-c PS₅ I wherein 0<

c<

1, and p-Cu₃ PS₄.

56. A photoelectrochemical cell according to claim 54, wherein said copper ion conductive solid electrolyte comprises a compound of the formula, Rb_j K_1-j Cu₄ I₁.5 Cl₃.5 in which 0.8≦

j≦

1.0.

57. A photoelectrochemical cell according to claim 54, wherein said Cu ion conductive solid electrolyte comprises a member selected from the group consisting of RbAg₄ I₅, RbCu₄ I₁.5 Cl₃.5 Rb₄.2 Cu₁₅.8 I₆.8 Cl₁₃.2, Rb₄.2 Cu₁₅.8 I₇.0 Cl₁₃.0, Rb₄.2 Cu₁₅.8 I₇.2 C₁₂.8, Rb₄.2 Cu₁₅.8 I₇.4 C₁₂.6, Rb₃.8 Cu₁₆.2 I₆.8 C₁₃.2, Rb₃.8 Cu₁₆.2 I₇.0 C₁₃.0, Rb₃.8 Cu₁₆.2 I₇.2 C₁₂.8, Rb₃.8 Cu₁₆.2 I₇.4 C₁₂.6, Rb₄.0 Cu₁₆ I₆.6 C₁₃.4, Rb₄.0 Cu₁₆ I₆.8 C₁₃.2, Rb₄.0 Cu₁₆ I₇.0 C₁₃.0, Rb₄.0 Cu₁₆ I₇.2 C₁₂.8, Rb₄.0 Cu₁₆ I₇.4 C₁₂.6 Rb₄.0 Cu₁₆ I₇.6 C₁₂.4, Rb₄.0 Cu₁₆ I₇.8 C₁₂.2, Rb₄.0 Cu₁₆ I₈.0 C₁₂.0, and mixtures thereof.

58. A photoelectrochemical cell according to claim 54, wherein said second and fourth current collectors comprise graphite.