# US 4,172,925 A · Photoelectrochemical cell > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,172,925 A - Document ID: US4172925A - Status: Granted - Kind: A - Application number: 05/880,071 - Filed: 1978-02-22 - Granted: 1979-10-30 - Earliest claimed: 1978-02-22 - Assignees: Refac Electronics Corporation; Grumman Aerospace Corporation - Inventors: Schoen-nan Chen; Michael A. Russak; Horst Witzke; Joseph Reichman; Satyendra K. Deb - Web page: https://patentgrep.com/patent/US4172925A ## CPC - H01M 14/005: {Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F)} - H01G 9/20: Light-sensitive devices - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10) ## Abstract Photoelectrochemical cell structures and methods of fabricaton are disclosed which provide for easily manufactured efficient energy conversion devices. The structures incorporate one or more chambers for the electrolyte, and utilize semiconductor photoelectrodes. In the plural chamber structure, the semiconductor may be opaque, and need not necessarily be a thin film. Specific dopants for the semiconductor provide for decreased dark current and increased open circuit voltage. Post deposition treatment is disclosed for the semiconductor to provide an increased shorting current. Increased sputtering wattage is provided to increase the short circuit current available from the cell. An electrolyte composition is described having improved performance at high light intensity. In a multi-chamber embodiment, the electrode placement causes the photoactive site to be at an end of the chamber removed from the irradiation window, thereby permitting the use of non-transparent photoelectrodes. A third embodiment is disclosed including two photoelectrodes, in combination with a properly selected electrolyte, to provide response to two different portions of the spectrum at an increase operating efficiency. A method and apparatus is disclosed for utilizing a photoelectrochemical cell of the type provided in a dual role, both for electrical conversion of impinging radiation and for heat utilization resulting therefrom. Finally, a multi-chamber, multi-electrolyte structure is disclosed providing electrical charge storage after termination of radiation. ## Claims ### Claim 1 A photoelectrochemical cell structure having a window for receiving electromagnetic radiation, comprising: (a) a composite photoactive electrode comprising: (i) a light-transmissive substrate, (ii) a light-transmissive conductor, and (iii) a polycrystalline semiconductor thin film, doped with zinc selenide, (b) a counterelectrode, (c) an electrolyte contacting said photoactive electrode and said counterelectrode, (d) a chamber for containing said electrolyte, (e) means connected to said electrodes for conducting electrical current generated by said cell, and (f) means in said cell for reducing photodissolution of said electrodes. ### Claim 2 (depends on 1) Apparatus as in claim 1 further comprising a tab on said composite electrode, for bonding conducting means thereto. ### Claim 3 (depends on 2) Apparatus as in claim 2 further comprising openings in said chamber for filling the chamber with said electrolyte. ### Claim 4 (depends on 1) Apparatus as recited in claim 1 wherein said thin film is chosen from the group consisting of CdS, CdSe, CdTe and GaAs. ### Claim 5 (depends on 1) Apparatus as in claim 1 wherein said chamber is sealed. ### Claim 6 (depends on 5) Apparatus as in claim 5 wherein said seal comprises a gasket spacer. ### Claim 7 (depends on 5) Apparatus as in claim 5 comprising fill-holes in said chamber. ### Claim 8 (depends on 1) Apparatus as in claim 1 wherein said electrolyte is one of the class of polychalcogenide electrolytes including polychalcogenide ions therein for reducing the photoelectrode against photodissolution. ### Claim 9 (depends on 8) Apparatus as in claim 8 wherein said polychalcogenide ions are sulfide ions at a concentration no less than 0.2 M. ### Claim 10 (depends on 8) Apparatus as in claim 8 wherein said polychalcogenide ions are selenium ions at a concentration no less than 0.2 M. ### Claim 11 (depends on 1) Apparatus as in claim 1 wherein said counterelectrode comprises one or more materials selected from the group consisting of C, Pt, Co, Ni, Fe, Pb, Cu, and the chalcogenides of Co, Ni, Fe, Pb and Cu. ### Claim 12 (depends on 11) Apparatus as in claim 11 wherein said counterelectrode provides a wall of the cell structure, opposing the structural support member comprised of the composite electrode. ### Claim 13 (depends on 1) Apparatus as in claim 1 wherein small bandgap materials are used for said photoactive electrodes, and wherein said electrolyte includes means for reducing photodissolution of said photoelectrodes. ### Claim 14 Photoelectrochemical cell structure comprising: (a) a window for receiving electromagnetic radiation, (b) first photoelectrode means, (c) second electrode means, (d) electrolyte contacting said electrodes, (e) means for placing at least one photoactive site at the junction of said photoelectrode and said electrolyte located between said window and said first electrode, comprising: (i) first chamber for said electrolyte, located between said first electrode and said window, (ii) second chamber for said electrolyte located between said first and second electrodes, and (iii) communicating means for said electrolyte between said first and second chambers, and (f) means within said cell for reducing photodissolution of said electrodes, (g) whereby said first electrode is not required to be light transmissive. ### Claim 15 (depends on 14) Apparatus as in claim 14 wherein said communicating means comprises passageways between said first and second chambers, said passageways being internal to said cell. ### Claim 16 (depends on 14) Apparatus as in claim 14 further comprising a storage electrode, a separate electrolyte chosen to reduce self discharge of said storage electrode, third chamber means for storing said separate electrolyte, and semi-permeable means interfacing said third chamber and one of said first and second chambers, whereby storage of electrical charge is effected. ### Claim 17 Photoelectrochemical cell having a window receiving electromagnetic radiation, comprising: (a) first photoactive electrode having a first light transmissive semiconductor layer for passing radiation of a predetermined portion of the electromagnetic spectrum, (b) second photoactive electrode having a second semiconductor layer responsive to radiation passed by said first photoactive electrode in said predetermined portion of the electromagnetic spectrum, (c) said first and second semiconductor layers being deposited on opposing sides of a single substrate, (d) counterelectrode means cooperative with said photoactive electrodes for generating electricity, (e) electrolyte means contacting said photoactive electrodes and said counterelectrode, and (f) wherein at least one of said first and second semiconductor layers is doped with zinc selenide. ### Claim 18 (depends on 17) Apparatus as in claim 17 wherein said photoactive electrode semiconductor layers are of materials having different bandgaps, the photoactive electrode with material having the smaller bandgap being further removed from said window than the other photoactive electrode. ### Claim 19 (depends on 18) Apparatus as in claim 18 wherein said electrolyte is chosen for passing radiation having wavelengths within the range of wavelengths passed by the first semiconductor layer and those effective on the second semiconductor layer. ### Claim 20 (depends on 18) Apparatus as in claim 18 further comprising switching means for providing various combinations of electrical outputs from said first and second photoactive electrodes to a load. ### Claim 21 (depends on 17) Apparatus as in claim 17 wherein said first photoelectrode semiconductor layer comprises CdS. ### Claim 22 (depends on 17) Apparatus as in claim 17 wherein said second photoelectrode semiconductor layer comprises CdSe. ### Claim 23 (depends on 22) Apparatus as in claim 22 wherein said first photoelectrode semiconductor layer comprises CdS. ### Claim 24 (depends on 17) Apparatus as in claim 17 wherein said first and second semiconductor layers are CdSe and CdTe, respectively. ### Claim 25 (depends on 17) Apparatus as in claim 17 wherein materials having bandgaps no greater than 2.4 eV are used for said photoactive electrodes, and wherein said electrolyte includes means for reducing photodissolution of said photoelectrodes. ### Claim 26 Photoelectrochemical cell having a window receiving electromagnetic radiation, comprising: (a) first photoactive electrode having a first light transmissive semiconductor layer for passing radiation of a predetermined portion of the electromagnetic spectrum, (b) second photoactive electrode having a second semiconductor layer responsive to radiation passed by said first photoactive electrode in said predetermined portion of the electromagnetic spectrum, (c) counterelectrode means cooperative with said photoactive electrodes for generating electricity, (d) electrolyte means contacting said photoactive electrodes and said counterelectrode, (e) a storage electrode, (f) a separate electrolyte chosen to reduce self discharge of said storage electrode, (g) a chamber for said separate electrolyte, (h) semi-permeable means interfacing said electrolyte and said separate electrolyte, (i) wherein at least one of said first and second semiconductor layers is doped with zinc selenide, and (j) whereby storage of electrical charge is effected. ### Claim 27 (depends on 26) Apparatus as in claim 26 wherein said storage electrode is comprised of Cd/Cd(OH).sub.2. ### Claim 28 Apparatus for photoelectrochemical conversion comprising: (a) a light transmissive window, (b) a photoelectrode comprising a semiconductor film on a conducting substrate, (c) a counterelectrode for production of electrical current in cooperation with said photoelectrode, (d) first electrolyte contacting said photoelectrode, (e) means within said first electrolyte for stabilizing said photoelectrode against dissolution, (f) first chamber for said first electrolyte, (g) a storage electrode comprising Cd/Cd(OH).sub.2, (h) second electrolyte contacting said storage electrode chosen to reduce self discharge of said storage electrode, (i) second chamber for said second electrolyte, and (j) semipermeable interfacing means contacting said first and said second electrolyte. ### Claim 29 Apparatus for photoelectrochemical conversion comprising: (a) a light transmissive window, (b) a photoelectrode comprising a semiconductor film on a conducting substrate, (c) a counterelectrode for production of electrical current in cooperation with said photoelectrode, (d) first electrolyte contacting said photoelectrode, (e) means within said first electrolyte for stabilizing said photoelectrode against dissolution, (f) first chamber for said first electrolyte, comprising first and second subchambers, said first and second subchambers providing communication for the electrolyte contained therein by means of passages disposed within said cell, (g) a storage electrode, (h) second electrolyte contacting said storage electrode chosen to reduce self discharge of said storage electrode, (i) second chamber for said second electrolyte, and (j) semipermeable interfacing means contacting said first and said second electrolyte. ### Claim 30 (depends on 29) Apparatus as in claim 29 wherein said photoelectrode and said substrate are transparent. ### Claim 31 (depends on 29) Apparatus as in claim 29 further comprising switching means for enabling storage, photovoltaic, and combined operation. ### Claim 32 Apparatus for photoelectrochemical conversion comprising: (a) a light transmissive window, (b) a photoelectrode comprising a semiconductor film mounted on a nontransparent conducting substrate, (c) a counterelectrode for production of electrical current in cooperation with said photoelectrode, (d) first electrolyte contacting said photoelectrode, (e) means within said first electrolyte for stabilizing said photoelectrode against dissolution, (f) first chamber for said first electrolyte, (g) a storage electrode, comprising Cd--Cd(OH).sub.2 (h) second electrolyte contacting said storage electrode chosen to reduce self discharge of said storage electrode, (i) second chamber for said second electrolyte, and (j) semipermeable interfacing means contacting said first and said second electrolyte. ### Claim 33 Photoelectrochemical cell comprising a window receiving electromagnetic radiation, comprising: (a) first photoactive electrode having a first light transmissive semiconductor layer for passing radiation of a predetermined portion of the electromagnetic spectrum, (b) second photoactive electrode having a second semiconductor layer responsive to radiation passed by said first photoactive electrode in said predetermined portion of the electromagnetic spectrum, (c) counterelectrode means cooperative with said photoactive electrodes for producing electricity, (d) electrolyte means contacting said photoactive electrodes and said counterelectrode, (e) a storage electrode comprising Cd/Cd(OH).sub.2, (f) a separate electrolyte chosen to reduce self discharge of said storage electrode, (g) a chamber for said separate electrolyte, and (h) semipermeable means interfacing said electrolyte and said separate electrolyte, (i) whereby storage of electrical charge is effected.