Conversion of solar energy to chemical and electrical energy

• US 4,215,182 A
• Filed: 05/29/1979
• Issued: 07/29/1980
• Est. Priority Date: 05/29/1979
• Status: Expired due to Term

• Current Assignee: International Power Ltd.
• Original Assignee: Institute Of Gas Technology (GTI Energy)
• Inventors: Sammells, Anthony F., Ang, Peter G. P.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/043,144
• Time in Patent Office: 427 Days
• Field of Search: 429/19, 429/111, 429/9, 429/17, 429/21, 429/15
• US Class Current: 429/500
• CPC Class Codes: H01M 8/18 Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Apparatus and processes for conversion of solar energy to chemical and electrical energy using a photoelectrochemical membrane cell to regenerate the redox anolyte of a redox-oxygen cell.

Claims

1. A process for conversion of solar energy to electrical energy by using a photoelectrochemical membrane cell to regenerate a redox anolyte of a redox-oxygen cell for production of electrical energy comprising in combination:

A. in a photoelectrochemical membrane cell;

illuminating photosensitizers with solar energy thereby producing excited sensitizers and electrons, said sensitizers being located in a redox electrolyte comprising R/O couples adjacent an electron transferring membrane separating said redox electrolyte from a redox aqueous anolyte comprising A⁺ⁿ /A^+n-1 couples, said redox electrolyte couples having a redox potential more negative than the decomposition potential of said sensitizers and said redox anolyte couples having redox potential more positive than the excited state level of the sensitizers or the flat-band potential of a semiconductor sensitizer,

passing said electrons through said membrane oxidizing said sensitizers and reducing said redox anolyte couples,

regenerating the oxidized sensitizers by reduction in said redox electrolyte producing oxidized redox electrolyte couples,

electrochemically regenerating oxidized redox electrolyte couples at the surface of a negative electrode in electronic communication with said redox electrolyte and in electronic communication through an external bias circuit with a positive electrode in electronic communication with said redox aqueous anolyte, and venting oxygen produced at said positive electrode,

B. passing said reduced redox aqueous anolyte couples to a redox-oxygen cell;

C. in said redox-oxygen cell;

passing said reduced redox anolyte couples in contact with a porous flowthrough anode thereby oxidizing said couples to a condition suitable for recycle to said photoelectrochemical membrane cell as electron acceptor redox anolyte couples,

passing oxygen through a diffusion cathode to a catholyte of said redox-oxygen cell to form water,

withdrawing electrical energy from said redox-oxygen cell by an external load circuit in electronic communication between said porous anode and said diffusion cathode, an ionically conductive separator between the redox-oxygen cell catholyte and anolyte completing the circuit; and

D. recycling said oxidized redox anolyte couples to the anolyte side of said photoelectrochemical membrane cell.

2. The process of claim 1 wherein said electron transferring membrane is derived from natural biological materials.

3. The process of claim 1 wherein said electron transferring membrane is synthetic material.

4. The process of claim 1 wherein said photosensitizers are n-type semiconductors.

5. The process of claim 4 wherein said n-type semiconductors are selected from the group consisting of GaAs, CdSe, MoS₂, Fe₂ O₃ and polyacetylene.

6. The process of claim 1 wherein said photosensitizers are selected from the group consisting of eosin Y, merocyanine 540, rose bengal, rhodamine B, phthalocyanine and nickel, copper, or cobalt phthalocyanine, [Ru (bipy)(bipy)₂ ] (ClO₄)₂ with long chain organic constituents, and [Rh₂ (1,3-diisocyanopropane)₄ Cl₂ ]²⁺.

7. The process of claim 1 wherein said R/O couples are selected from the group consisting of Ti⁺³ /Ti⁺⁴, I^- /I₂, C₆ H₄ (OH)₂ /C₆ H₄ O₂, and BrC₆ H₃ (OH)₂ /BrC₆ H₃ O₂.

8. The process of claim 1 wherein said A⁺ⁿ /A^+n-1 couples are selected from the group consisting of H⁺ /H₂, Cr⁺² /Cr⁺³, Ti⁺² /Ti⁺³, Cu⁺ /Cu⁺², Sn⁺² /Sn⁺⁴, Te^-2 /Te₂^-2 and I^- /I₂.

9. The process of claim 1 wherein said redox electrolyte and said redox anolyte is an aqueous basic electrolyte selected from the group consisting of KOH, NaOH and NH₄ OH.

10. The process of claim 1 wherein said redox electrolyte and said redox anolyte is an aqueous acid electrolyte selected from the group consisting of H₂ SO₄, HCl, H₃ PO₄ and C₂ H₄ O₂.

11. The process of claim 1 wherein an external bias voltage of about 80 mV to about 150 mV is provided.

12. In a process for conversion of solar energy to electrical energy by using a photoelectrochemical membrane cell to regenerate a redox anolyte of a redox-oxygen cell for production of electrical energy, the steps comprising:

illuminating photosensitizers with solar energy thereby producing excited sensitizers and electrons, said sensitizers being located in a redox electrolyte comprising R/O couples on or within an electron transferring membrane separating said redox electrolyte from a redox aqueous anolyte comprising A⁺ⁿ /A^+n-1 couples, said redox electrolyte couples having a redox potential more negative than the decomposition potential of said sensitizers and said redox anolyte couples having redox potential more positive than the excited state level of the sensitizers or the flat-band potential of a semiconductor sensitizer;

passing said electrons through said membrane thereby oxidizing said sensitizers and reducing said redox anolyte couples;

regenerating the oxidized sensitizers by reduction in said redox electrolyte thereby producing oxidized redox electrolyte couples; and

electrochemically regenerating oxidized redox electrolyte couples at the surface of a negative electrode in electronic communication with said redox electrolyte and in electronic communication through an external bias circuit with a positive electrode in electronic communication with said redox aqueous anolyte, and venting oxygen produced at said positive electrode.

13. The process of claim 12 wherein said electron transferring membrane is derived from natural biological materials.

14. The process of claim 12 wherein said electron transferring membrane is synthetic material.

15. The process of claim 12 wherein said photosensitizers are n-type semiconductors.

16. The process of claim 15 wherein said n-type semiconductors are selected from the group consisting of GaAs, CdSe, MoS₂, Fe₂ O₃ and polyacetylene.

17. The process of claim 12 wherein said photosensitizers are selected from the group consisting of eosin Y, merocyanine 540, rose bengal, rhodamine B, phthalocyanine and nickel, copper or cobalt phthalocyanine, [Ru (bipy)(bipy)₂ ] (ClO₄)₂ with long chain organic constituents, and [Rh₂ (1,3-diisocyanopropane)₄ Cl₂ ]²⁺.

18. The process of claim 12 wherein said R/O couples are selected from the group consisting of Ti⁺³ /Ti⁺⁴, I^- /I₂, C₆ H₄ (OH)₂ /C₆ H₄ O₂, and BrC₆ H₃ (OH)₂ /BrC₆ H₃ O₂.

19. The process of claim 12 wherein said A⁺ⁿ /A^+n-1 couples are selected from the group consisting of H⁺ /H₂, Cr⁺² /Cr⁺³, Ti⁺² /Ti⁺³, Cu⁺ /Cu⁺², Sn⁺² /Sn⁺⁴, Te^-2 /Te₂^-2 and I^- /I₂.

20. The process of claim 12 wherein said redox electrolyte and said redox anolyte is an aqueous basic electrolyte selected from the group consisting of KOH, NaOH and NH₄ OH.

21. The process of claim 12 wherein said redox electrolyte and said redox anolyte is an aqueous acid electrolyte selected from the group consisting of H₂ SO₄, HCl, H₃ PO₄ and C₂ H₄ O₂.

22. The process of claim 12 wherein an external bias voltage of about 80 mV to about 150 mV is provided.

23. A process for converting solar energy to chemical energy using a photoelectrochemical membrane cell comprising the steps of:

illuminating photosensitizers with solar energy thereby producing excited sensitizers and electrons, said sensitizers being located in a redox electrolyte comprising R/O couples adjacent an electron transferring membrane separating said redox electrolyte from a redox aqueous anolyte comprising A⁺ⁿ /A^+n-1 couples, said redox electrolyte couples having a redox potential more negative than the decomposition potential of said sensitizers and said redox anolyte couples having redox potential more positive than the excited state level of the sensitizers or the flat-band potential of a semiconductor sensitizer;

passing said electrons through said membrane thereby oxidizing said sensitizers and reducing said redox anolyte couples;

regenerating the oxidized sensitizers by reduction in said redox electrolyte thereby producing oxidized redox elctrolyte couples;

electrochemically regenerating oxidized redox electrolyte couples at the surface of a negative electrode in electronic communication with said redox electrolyte and in electronic communication through an external bias circuit with a positive electrode in electronic communication with said redox aqueous anolyte, and venting oxygen produced at said positive electrode; and

removing said reduced redox aqueous anolyte couples from said membrane cell for energy utilization.

24. The process of claim 23 wherein said electron transferring membrane is derived from natural biological materials.

25. The process of claim 23 wherein said electron transferring membrane is synthetic material.

26. The process of claim 23 wherein said photosensitizers are n-type semiconductors.

27. The process of claim 26 wherein said n-type semiconductors are selected from the group consisting of GaAs, CdSe, MoS₂, Fe₂ O₃ and polyacetylene.

28. The process of claim 23 wherein said photosensitizers are selected from the group consisting of eosin Y, merocyanine 540, rose bengal, rhodamine B, phthalocyanine and nickel copper or cobalt phthalocyanine, [Ru (bipy)(bipy)₂ ] (ClO₄)₂ with long chain organic constituents, and [Rh₂ (1,3-diisocyanopropane)₄ Cl₂ [²⁺.

29. The process of claim 23 wherein said R/O couples are selected from the group consisting of Ti⁺³ /Ti⁺⁴, I^- /I₂, C₆ H₄ (OH)₂ /C₆ H₄ O₂, and BrC₆ H₃ (OH)₂ /BrC₆ H₃ O₂.

30. The process of claim 23 wherein said A⁺ⁿ /A^+n-1 couples are selected from the group consisting of H⁺ /H₂, Cr⁺² /Cr⁺³, Ti⁺² /Ti⁺³, Cu⁺ /Cu⁺², Sn⁺² /Sn⁺⁴, Te^-2 /Te₂^-2 and I^- /I₂.

31. The process of claim 23 wherein said redox electrolyte and said redox anolyte is an aqueous basic electrolyte selected from the group consisting of KOH, NaOH and NH₄ OH.

32. The process of claim 23 wherein said redox electrolyte and said redox anolyte is an aqueous acid electrolyte selected from the group consisting of H₂ SO₄, HCl, H₃ PO₄ and C₂ H₄ O₂.

33. The process of claim 23 wherein an external bias voltage of about 80 mV to about 150 mV is provided.

34. A photoelectrochemical membrane cell comprising:

a cell container divided into a first and second compartment by an electron transferring membrane comprising photosensitizers on said first compartment side;

a redox electrolyte comprising R/O couples in said first compartment and a redox aqueous anolyte comprising A⁺ⁿ /A^+n-1 couples in said second compartment, said redox electrolyte couples having a redox potential more negative than the decomposition potential of said sensitizers and said redox anolyte couples having a redox potential more positive than the excited state level of the sensitizers or the flat-band potential of a semiconductor sensitizer;

a negative electrode in electronic communication with said redox electrolyte and in electronic communication through an external bias circuit with a positive electrode in electronic communication with said redox aqueous anolyte.

35. The photoelectrochemical cell of claim 34 wherein said electron transferring membrane is derived from natural biological materials.

36. The photoelectrochemical cell of claim 34 wherein said electron transferring membrane is synthetic material.

37. The photoelectrochemical cell of claim 34 wherein said photosensitizers are n-type semiconductors.

38. The photoelectrochemical cell of claim 37 wherein said n-type semiconductors are selected from the groupconsisting of GaAs, CdSe, MoS₂, Fe₂ O₃ and polyacetylene.

39. The photoelectrochemical cell of claim 34 wherein said photosensitizers are selected from the group consisting of eosin Y, merocyanine 540, rose bengal, rhodamine B, phthalocyanine and nickel, copper or cobalt phthalocyanine, [Ru (bipy)(bipy)₂ ] (ClO₄)₂ with long chain organic constituents, and [Rh₂ (1,3-diisocyanopropane)₄ Cl₂ ]²⁺.

40. The photoelectrochemical cell of claim 34 wherein said R/O couples are selected from the group consisting of Ti⁺³ /Ti⁺⁴, I^- /I₂, C₆ H₄ (OH)₂ /C₆ H₄ O₂, and BrC₆ H₃ (OH)₂ /BrC₆ H₃ O₂.

41. The photoelectrochemical cell of claim 34 wherein said A⁺ⁿ /A^+n-1 couples are selected from the group consisting of H⁺ /H₂, Cr⁺² /Cr⁺³, Ti⁺² /Ti⁺³, Cu⁺ /Cu⁺², Sn⁺² /Sn⁺⁴, Te^-2 /Te₂^-2 and I^- /I₂.

42. The photoelectrochemical cell of claim 34 wherein said redox electrolyte and said redox anolyte is an aqueous basic electrolyte selected from the group consisting of KOH, NaOH, and NH₄ OH.

43. The photoelectrochemical cell of claim 34 wherein said redox electrolyte and said redox anolyte is an aqueous acid electrolyte selected from the group consisting of H₂ SO₄, HCl, H₃ PO₄ and C₂ H₄ O₂.