Tandem cell for water cleavage by visible light

• US 6,936,143 B1
• Filed: 04/07/2000
• Issued: 08/30/2005
• Est. Priority Date: 07/05/1999
• Status: Expired due to Fees

• Current Assignee: Ecole polytechnique fãdãrale de lausanne epfl (Schweizerische Eidgenossenschaft)
• Original Assignee: Ecole polytechnique fãdãrale de lausanne epfl (Schweizerische Eidgenossenschaft)
• Inventors: Augustynski, Jan, Graetzel, Michael
• Primary Examiner(s): Valentine, Donald R.
• Application Number:
  US10/030,036
• Time in Patent Office: 1,971 Days
• Field of Search: 204/242, 204265-266, 204/290.01, 204277-278, 204/258, 204/270
• US Class Current: 204/242
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A tandem cell or photoelectrochemical system for the cleavage of water to hydrogen and oxygen by visible light has two superimposed photocells, both cells being connected electrically. The photoactive material in the top cell is a semiconducting oxide placed in contact with an aqueous solution. This semiconducting oxide absorbs the blue and green part of the solar emission spectrum of a light source or light sources and generates with the energy collected oxygen and protons from water. The not absorbed yellow and red light transmits the top cell and enters a second photocell, the bottom cell, which is mounted, in the direction of the light behind, preferably directly behind the top cell. The bottom cell includes a dye-sensitized mesoporous photovoltaic film. The bottom cell converts the yellow, red and near infrared portion of the sunlight to drive the reduction of the protons, which are produced in the top cell during the photo catalytic water oxidation process, to hydrogen.

Claims

1. A photoelectrochemical system for the cleavage of water to hydrogen and oxygen by visible light comprising first and second superimposed top and bottom photocells, the cells being connected electrically, a photoactive material in the top cell being a semiconducting oxide placed in contact with an aqueous solution, the oxide absorbing a blue and green part of the solar emission spectrum to generate oxygen and protons from water and transmitting a yellow and red part of the solar emission spectrum light to the bottom photocell mounted behind the top cell and composed of a sensitizer comprising a dye-sensitized porous photovoltaic film, said bottom cell converting the yellow and red parts and a near infrared part of the solar emission spectrum to drive the reduction of the protons, produced in the top cell during a photo catalytic water oxidation process, to hydrogen.

2. A photoelectrochemical system for the direct cleavage of water to hydrogen and oxygen by visible light according to claim 1 comprising two superimposed photocells, both cells being connected electrically, wherein the photoactive material present in the top photocell is a thin film of WO₃ or Fe₂O₃ deposited on a conducting substrate or conducting glass and placed in contact with an aqueous electrolyte solution, said WO₃ tungsten oxide or Fe₂O₃ iron oxide absorbing the blue and green part of the solar emission spectrum to generate oxygen and protons from water and transmitting the yellow and red light to the bottom photocell mounted behind the top photocell and composed of the dye-sensitized photovoltaic film, said bottom photocell converting the yellow, red and near infrared parts of the solar emission spectrum to drive the reduction of the protons, produced in the top photocell during the water oxidation process, said reduction of protons to hydrogen gas taking place in an electrolyte compartment mounted behind the bottom photocell and being separated from the top photocell compartment where oxygen is evolved by a glass frit or an ion conducting membrane.

3. A photoelectrochemical system according to claim 1, characterized in that the photoactive oxide material present in the top cell is a doped form of Fe₂O₃, the dopant being selected from the elements Si, Ge, Sn, Pb, Ti, Zr, Hf, Sb, Bi, V, Nb, Ta, Mo, Tc and Re or F, Cl, Br and I.

4. A photoelectrochemical system according to claim 1, characterized in that a photoactive Fe₂O₃ in doped or undoped form is present as a smooth layer, said layer having a thickness between 50 nm and 5000 nm, said layer transmitting light of wavelength above 600 nm.

5. A photoelectrochemical system according to claim 1, characterized in that the sensitizer is a ruthenium polypyridyl complex chosen from RuL₂(NCS)₂ and RuL′

(NCS)₃, where L=4,4′

-dicarboxy-2,2′

-bipyridine and L′

=4,4′

4″

-tricarboxy-2,2′

,6′

,2″

-terpyridine.

6. A photoelectrochemical system according to claim 1, characterized in that the oxygen and hydrogen evolution reaction take place both in the top cell and/or in separated compartments, said compartments being connected by an ion conducting membrane or a glass frit.

7. A photoelectrochemical system according to claim 1, characterized in that the hydrogen evolution is catalyzed by a metal, chosen from Ni, Pt, Pd, Ru, Rh and Ir, or alternatively by a polyacid or heteropolyacid chosen from tungsten, vanadium and molybdenum, said catalyst being deposited in the form of a thin coating on the cathode of the cell.

8. A photoelectrochemical system according to claim 1, characterized in that seawater is used as a source for hydrogen and oxygen in a water cleavage or water splitting device.