# US 4,400,451 A · Solar energy converter > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,400,451 A - Document ID: US4400451A - Status: Granted - Kind: A - Application number: 06/259,917 - Filed: 1981-05-04 - Granted: 1983-08-23 - Earliest claimed: 1981-05-04 - Assignees: Diamond Shamrock Corporation - Inventors: Arnold Z. Gordon - Web page: https://patentgrep.com/patent/US4400451A ## CPC - C25B 1/55: Photoelectrolysis - H01G 9/20: Light-sensitive devices - H01M 6/181: {with polymeric electrolytes} - H01M 14/005: {Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F)} - Y02E 10/549: Organic PV cells - Y02P 20/133: Renewable energy sources, e.g. sunlight - C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B) - 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) - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract Liquid-junction photoelectrochemical semiconductor cells adapted for providing electricity, fuel, chemicals and/or chemical energy, preferably solar cells, which utilize a photoactive true solid/solid solution semiconductor mixed metal oxide material bulk or film electrode. Useful electrolytes include liquid, sol, gel or a solid electrolyte system, e.g., a film of an ionomer or of a polymer solvated with a liquid electrolyte. ## Claims ### Claim 1 A liquid-junction photoelectrochemical semiconductor cell adapted for producing electricity, fuel, chemicals and/or chemical energy by use of light radiation comprising: (I) a first electrode comprising: a bulk or film electrode comprising a photoactive true solid/solid solution semiconductor material having a band gap of approximately 1.4 eV and which, in the case of a film electrode, is disposed on a supporting electrically conductive substrate; (II) a second electrode comprising: a semiconductive or conductive layer which is transparent to radiation of energy corresponding to the band gap of said first electrode (I), and which is disposed on a supporting conductive substrate, wherein said substrate also is transparent to radiation of energy corresponding to the band gap of component (I), further characterized in that said second electrode, if a semiconductor, is of opposite conductivity type in relation to said first electrode; (III) an electrolyte disposed between, and in intimate contact with, both components (I) and (II); (IV) a means for receiving the electrical energy produced; wherein component (I) is further characterized in that said semiconductor material thereof is a photoactive true solid/solid solution mixed metal oxide semiconductor material derived from precursor substances selected from the group consisting of elemental metals, non-oxide metal compounds, and mixtures thereof; said phhotoactive true solid/solid solution mixed metal oxide semiconductor material corresponding to the formula A.sub.r.sup.ya M.sub.y.sup.vm O.sub.z.sup.-2 ; where said formula represents the stoichiometry of the basic repeating unit lattice cell; where M is the combination of component (a) metal and component (b) metal; A when present is at least one different metal which does not substantially alter the optical absorption accruing from M in the above formula; O represents oxygen, said formula being further characterized in that r, y, z, va and vm are defined by the relationship va(r)+vm(y)=2z, wherein r equals a value of from 0 to 2, inclusive, y is from 1 to 2, inclusive, z is from 1 to 7, inclusive, va equals the positive valence of A, vm equals the positive mean valence of M, and the valence of oxygen is -2; and wherein all said metal components of said formula are selected from the group consisting of boron, aluminum, tin, lead, the transition metals of families 1b through 7b, inclusive, and 8 of the periodic table of elements, and the lanthanide series; wherein M in the above formula comprises: (a) 50 to 99.9 mole percent, based on the total metals mole fraction, of one or more component (a) metals; and (b) 0.1 to 50 mole percent, based on the total metals mole fraction, of one or more component (b) metals; with the proviso that said component (b) metals are different than said component (a) metals and with the further proviso that said component (a) metals, when in comparable oxide form, have a larger band gap that said component (b) metals, when said component (b) metals are in their comparable oxide form; wherein said photoactive true solid/solid solution mixed metal oxide material's optical absorption edge is thereby optimized to approximately 1.4 eV. ### Claim 2 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said electrolyte is maintained in intimate contact with said electrodes by immersion of said electrodes in said electrolyte. ### Claim 3 (depends on 2) A photoelectrochemical cell as claimed in claim 2 wherein said electrolyte is selected from the group consisting of liquids, sols and gels. ### Claim 4 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said component III is a solid electrolyte system comprising an ionomer or polymer solvated with a liquid electrolyte capable of redox chemistry. ### Claim 5 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said electrolyte is an aqueous redox couple in a solvent. ### Claim 6 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein a containing means is provided to contain said electrolyte. ### Claim 7 (depends on 6) A photoelectrochemical cell as claimed in claim 6 wherein said containing means is selected from the group consisting of glass, ceramic, metals, coated metals, plastic, a glass fiber filled resin material and combinations thereof. ### Claim 8 (depends on 6) A photoelectrochemical cell as claimed in claim 6 wherein said containing means is selected from the group consisting of a tetrafluoroethylene (TFE), a polyvinyl chloride (PVC) and a post-chlorinated polyvinyl chloride (CPVC). ### Claim 9 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said means for receiving said electrical energy is selected from the group consisting of an electrical circuit, a storage means and combinations thereof. ### Claim 10 (depends on 9) A photoelectrochemical cell as claimed in claim 9 wherein said storage means is a battery. ### Claim 11 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, r is 0, y is 1, z is 2 and the final oxide corresponds to the formula MO.sub.2. ### Claim 12 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, r is 1, y is 1, z is 3 and the final oxide compound corresponds to the formula AMO.sub.3. ### Claim 13 (depends on 1) A photoelectochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, r is 2, y is 2, z is 7 and the final oxide compound corresponds to the formula A.sub.2 M.sub.2 O.sub.7. ### Claim 14 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, r is 0, y is 2, z is 3 and the final oxide compound corresponds to the formula M.sub.2 O.sub.3. ### Claim 15 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, r is 0, y is 1, z is 1 and the final oxide compound corresponds to the formula MO. ### Claim 16 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, A is a single metal selected from the group consisting of strontium, zinc and the lanthanides. ### Claim 17 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, A is a combination of from 2 to 3 different metals selected from the group consisting of strontium, zinc and the lanthanides. ### Claim 18 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, M is a combination of two different metals selected from the group consisting of boron, aluminum, tin, lead, the lanthanide series and the transition metals. ### Claim 19 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, M is a combination of titanium and a metal selected from the group consisting of Rh, Ru, Ir, Mn, Cr, Fe, V and Pt. ### Claim 20 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, M is a combination of aluminum and a metal selected from the group consisting of Rh, Ru, Ir, Mn, Cr, Fe, V and Pt. ### Claim 21 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, M is a combination of Ru or Rh and one metal selected from the group consisting of niobium, lanthanum, tantalum, tin, titanium and zirconium. ### Claim 22 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein for said formula of component I semiconductor material, M is a combination of 3 to 4 different metals characterized in that one metal is selected from the grup Al, Nb, La, Ta, Sn, Ti and Zr and the remaining different metals are selected from the group consisting of Ir, Mn, Cr, Fe, V, Pt, Rh and Ru. ### Claim 23 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said substrate of component II is selected from the group consisting of glass, tetrafluoroethylene (TFE), PVC, CPVC, fluorinated ethylene-propylene resin (FEP), polyvinylidene difluoride (PVDF), poly-(methylmethacrylate)-type polymers, silicone, silicates, transparent inorganic materials, transparent organic materials or combinations thereof. ### Claim 24 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said substrate of component I is selected from the group consisting of a valve metal, a precious metal, other suitable metal, ceramic, glass and combinations thereof. ### Claim 25 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said substrate of component I is selected from the group consisting of titanium, zirconium and tin. ### Claim 26 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said component I is a bulk electrode of said photoactive true solid/solid semiconductor mixed metal oxide material. ### Claim 27 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said electrolyte is an aqueous solution of NaOH saturated with oxygen. ### Claim 28 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said first electrode comprises a single layer of said true solid/solid solution metal oxide material. ### Claim 29 (depends on 1) A photoelectrochemical cell as claimed in claim 1 wherein said first electrode comprises at least two layers of said true solid/solid solution metal oxide material. ### Claim 30 (depends on 1, 2) A photoelectrochemical cell as claimed in claims 1 or 2 wherein component IV is one or more means selected from the group consisting of a means for collecting the fuel produced, a means for collecting the chemical energy produced and a means for collecting chemicals produced.