US20070246370A1 - Device and Method for Photovoltaic Generation of Hydrogen - Google Patents

Device and Method for Photovoltaic Generation of Hydrogen Download PDF

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Publication number
US20070246370A1
US20070246370A1 US11/576,939 US57693905A US2007246370A1 US 20070246370 A1 US20070246370 A1 US 20070246370A1 US 57693905 A US57693905 A US 57693905A US 2007246370 A1 US2007246370 A1 US 2007246370A1
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hydrogen
solar cell
containing compounds
electrolysis
cathode
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US11/576,939
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English (en)
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Frank Dimroth
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of US20070246370A1 publication Critical patent/US20070246370A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/052—Cooling means directly associated or integrated with the PV cell, e.g. integrated Peltier elements for active cooling or heat sinks directly associated with the PV cells
    • H01L31/0521—Cooling means directly associated or integrated with the PV cell, e.g. integrated Peltier elements for active cooling or heat sinks directly associated with the PV cells using a gaseous or a liquid coolant, e.g. air flow ventilation, water circulation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a device and a method for the photo-voltaic generation of hydrogen from hydrogen-containing compounds, sunlight being concentrated on solar cells by means of an optical concentrator and the consequently generated voltage being used directly for the electrolysis of a hydrogen-containing compound, in particular of deionised water, in order to generate hydrogen.
  • Solar hydrogen can be obtained with the help of biological water splitting by bacteria, photoelectrochemical cells, from biomass reforming or by solar thermal splitting of water at high temperatures.
  • a device for the photovoltaic generation of hydrogen from hydrogen-containing compounds which consists of a plurality of units which track the position of the sun, which device has an optical concentrator for concentrating sunlight onto a solar cell, at least one solar cell which is not in contact with the hydrogen-containing compounds and is electrically connected to an electrolysis unit which has an anode and a cathode in contact with the hydrogen-containing compounds, the units being disposed on a tracking system following the position of the sun.
  • the system underlying the present invention is characterised by the integration of solar power generation and hydrogen production in one system and hence by a lower material and spatial requirement, higher efficiency and potentially lower costs for the solar hydrogen.
  • electrical losses which are normally produced by the wiring of solar cells in a module are hence dispensed with.
  • a substantial advantage relative to photoelectro-chemical methods is based on the fact that the photovoltaic cell is not in direct contact with the electrolyte. This can otherwise lead to significant problems, such as e.g. the oxidation of semi-conductor layers or the removal or deposition of material by the electrolysis. This extends the long term stability of such systems.
  • optical absorption losses of the sunlight in the hydrogen-containing compound are avoided.
  • each individual unit of the device has an electrical power of 1 to 100 W.
  • the electrolysis unit according to the invention preferably has an operating temperature of ⁇ 10° C. to 200° C., particularly preferred of 30° C. to 100° C.
  • a point-focusing lens such as e.g. a Fresnel lens, is used preferably as optical concentrator.
  • a curved Fresnel lens with a line focus, a parabolic mirror with a line focus or a dished mirror with a point focus can be used.
  • the solar cell is preferably constructed from a plurality of layers made of semiconductor materials which are connected to each other in series and have respectively different band gap energy.
  • the semiconductor materials are thereby preferably selected from the group consisting of silicon, germanium and the III-V compounds of aluminium, gallium or indium with nitrogen, phosphorus, arsenic or antimony.
  • the polarity of the solar cell is freely selectable so that both an np polarity and a pn polarity is possible.
  • the solar cell if merely a pn or np transition is present, can have a voltage of more than 1.4 volts, particularly preferred of 1.6 to 2.4 volts. If the solar cell has a plurality of series-connected pn or np transitions, then a voltage in the range of 1.5 to 6 volts can be achieved.
  • the solar cell thereby preferably has an area of 0.01 to 1 cm squared.
  • PEM proton-permeable polymer membrane
  • the anode and the cathode consist of noble metals, in particular here platinum, palladium or iridium, the compounds thereof, e.g. iridium oxide, or of metals coated with noble metal, in particular here nickel, iron or copper. These materials also serve as catalyst for the electrolysis.
  • the electrodes can preferably have in addition a distribution structure which is disposed on the electrodes in order to distribute the current. This is preferably a metal grating.
  • a further variant of the device according to the invention provides that the anode is connected to a channel system through which the hydrogen-containing compounds flow.
  • the cathode is likewise connected to a channel system or to a gas-permeable material through which the generated hydrogen is discharged.
  • a further embodiment of the device according to the invention provides that the electrolysis unit consists of two or more units which are connected to each other in series and have a correspondingly higher operating voltage.
  • a method for the generation of hydrogen from hydrogen-containing compounds in which sunlight is concentrated on at least one solar cell by means of an optical concentrator and, with the photovoltaically generated voltage, the hydrogen-containing compounds are electrolysed at a temperature preferably in the range of ⁇ 10° C. to 200° C., particularly preferred of 30° C. to 100° C., the solar cell being contacted electrically with an electrolysis unit with a cathode and/or an anode and the protons formed by the electrolysis being conducted from the anode to the cathode where they are reduced to form molecular hydrogen.
  • a preferred embodiment of the method according to the invention provides that the hydrogen-containing compounds are also used for cooling in that the hydrogen-containing compounds are made to flow along the solar cell.
  • the hydrogen-containing compound contains deionised water in substantial parts. In this case, it is then also possible to generate also oxygen in addition to hydrogen.
  • FIG. 1 shows a schematic representation of the method for generating hydrogen according to the invention.
  • FIG. 2 shows a first embodiment of the device according to the invention.
  • FIG. 3 shows a device for photovoltaic generation of hydrogen as an overall system according to the invention.
  • FIG. 4 shows schematically the principle of energy conversion in the method according to the invention for generating hydrogen.
  • FIG. 5 shows a second embodiment of the device according to the invention.
  • FIG. 6 shows a third embodiment of the device according to the invention.
  • FIG. 7 shows the schematic construction of a device according to the invention in which an electrolysis unit is combined with a plurality of solar cells.
  • the system is represented schematically, which can generate hydrogen efficiently by the electrolysis of hydrogen-containing compounds, e.g. aqueous solutions, such as deionised water, with the help of photovoltaically generated energy.
  • This system consists of a concentrator 2 which concentrates the sunlight 1 onto a solar cell 3 .
  • the concentration factor of the sunlight can thereby be in the range of 50 and approx. 1500.
  • concentrations of sunlight here are in the range of 300 and 1000.
  • a solar cell 3 which converts the sunlight into electrical power is situated at the focal point of the concentrator 2 . Voltages>1.4 volts, as are necessary for the electrolysis, are hereby generated at the operating point of the solar cell.
  • solar cells made of III-V semiconductors having one or more pn or np transitions As cascade solar cells, for example those made of GaInP/GaInAs or AlGaInAs/Ge can be used.
  • the band gaps of the solar cells should hereby be chosen such that the current-voltage characteristic line of the cell, with the concentrated solar spectrum, achieves as high as possible an efficiency for the electrolysis of the hydrogen-containing compounds.
  • the polarity of the solar cell can both be p to n and n to p.
  • the voltage applied to the solar cell 3 is used directly for the electrolysis of the hydrogen-containing compounds 5 .
  • the p and n conducting layers of the solar cells are connected directly to the electrodes of the electrolysis unit 4 .
  • the thereby produced hydrogen 6 is discharged and stored. If water is used for the electrolysis, then oxygen can also be obtained as further gas.
  • Each individual solar cell in the system illustrated in FIG. 1 is connected directly to an electrolysis unit. It is however also possible that up to 4 solar cells or even more are connected directly to a single electrolysis unit. Furthermore, it is possible that the electrolysis unit consists of two electrolysis units which are connected in series one behind the other, as a result of which the operating voltage is doubled.
  • the integration of a plurality of separate concentrator-solar cells-electrolysis unit units in an overall system is essential for the invention. These units then can (but need not) be completely separated from each other electrically. They are thereby disposed on a tracking unit and track the sun.
  • FIG. 2 A first embodiment of a device according to the invention for the photovoltaic generation of hydrogen is illustrated in FIG. 2 .
  • This device consists of a Fresnel lens 2 which concentrates the sunlight 1 by a factor 300 or more and directs it onto a cascade solar cell 3 made of III-V semiconductors.
  • the surface area of the solar cell is thereby between 0.01 to 1 cm 2 .
  • the concentrated sunlight is converted into electrical energy with high efficiency of more than 30%.
  • the voltage of the solar cell at the operating point is thereby >1.4 volts.
  • III-V materials have not been used for terrestrial energy generation to date since they are too expensive. By using concentrated light, the semiconductor surface is however significantly reduced and use becomes economical. In future, this is intended also to be used for solar power generation on earth.
  • the Fraunhofer ISE has been working in this context for some years on the so-called FLATCONTM concentrator. This system likewise uses cascade solar cells with concentrated sunlight for the generation of electrical power.
  • a cascade solar cell In a cascade solar cell, a plurality of layers made of III-V semi-conductors of different band gap energy are deposited one on the other. These partial cells are monolithically, i.e. on the substrate, connected in series to each other. As a result, operating voltages between 1 volt for a single solar cell and approx. 6 volts for a solar cell with 5-6 series-connected pn transitions can be achieved. Solar cells with 3 pn transitions have achieved efficiencies of up to 37% for the conversion of concentrated sunlight into electrical energy (R. King et al. “Metamorphic III-V Materials” Proc. of 19 th European Photovoltaic Solar Energy Conference Paris 2004).
  • band gaps and materials for the application described here must be reoptimised with respect to maximisation of the efficiency for the electrolysis of water.
  • Examples of possible material combinations are for example GaInP/GaInAs, GaAs/Ge, AlGaInAs/Ge, AlGaAs/Si, GaInP/GaInAs/Ge, AlGaInP/GaAs/GaInNAs/Ge or AlGaInP/GaIn/AlGaInAs/GaInAsN/Ge.
  • a further advantage in the use of concentrated light resides in the fact that the voltage of a solar cell increases logarithmically with the concentration.
  • the front and rear contact of the solar cell is connected directly via a metal grating 6 to electrodes (e.g. made of noble metals, such as platinum, palladium, iridium or iridium oxide which serve also as catalyst for the electrolysis, or made of nickel, iron or copper electrodes which are coated with such noble metals) on a proton-permeable polymer membrane (PEM) 4 .
  • electrodes e.g. made of noble metals, such as platinum, palladium, iridium or iridium oxide which serve also as catalyst for the electrolysis, or made of nickel, iron or copper electrodes which are coated with such noble metals
  • PEM proton-permeable polymer membrane
  • the surface of the PEM membrane can extend up to the total surface of incidence of the sunlight (apart from the surface of the solar cell).
  • the PEM membrane can however also adopt only a much smaller surface area.
  • the membrane is on the positive side of the anode in direct contact with the hydrogen-containing solution which consists of e.
  • the solution will firstly flow through below the solar cells in one possible arrangement and contributes there to the cooling. As a result, the efficiency of the solar cells can be increased. Subsequently, the solution is conducted through a channel system to the anode and is split there into oxygen and hydrogen ions. The oxygen molecules produced on the anode side rise within the liquid and can be collected there. The H + ions migrate through the PEM membrane to the negative cathode where they react with respectively two electrons to form molecular hydrogen. The cathode side is covered in turn with a channel system through which the hydrogen-containing solution flows or with a gas-permeable or porous material through which the hydrogen can be conducted to the store.
  • FIG. 3 shows a device 1 according to the invention which is assembled to form an overall system for photovoltaic generation of hydrogen.
  • the gases are collected here at the upper edge of the individual modules and supplied to a store 3 .
  • This store can consist of e.g. compressed gas cylinders.
  • the inflow pipe to the modules can be evacuated.
  • the modules are mounted on a 2-axis tracking unit 2 which follows the course of the sun. This is necessary to retain the focus of the lens always precisely on the solar cell. Since PEM electrolysis units achieve degrees of efficiency of 80 to 90%, with the system described here made of III-V cascade solar cells and PEM electrolysis unit, system degrees of efficiency of 27% can be achieved for the generation of hydrogen by means of sunlight.
  • the principle of energy conversion is represented schematically in FIG. 4 .
  • a hydrogen-containing compound is guided along the anode for example through a channel.
  • the result hereby is then splitting of water into oxygen and protons.
  • the protons can in turn pass through the proton-permeable polymer membrane (PEM) and thus reach the cathode.
  • PEM proton-permeable polymer membrane
  • the result here is reduction of the protons to form molecular hydrogen.
  • the polymer membrane is disposed adjacent to the solar cell.
  • the solar cell can be cooled from the rear by a channel through which cooling water flows.
  • FIG. 5 shows a further embodiment of the invention in which the PEM electrolysis unit 4 is disposed under the solar cell 3 .
  • the water flows here directly through channels 5 below the solar cell which are soldered on a Cu plate 6 .
  • the Cu plate can thereby be separated electrically by an insulator from the water.
  • Good thermal contact between the water for the electrolysis and the solar cell is produced. Hydrogen and oxygen are conveyed in this case as gas bubbles in the liquid.
  • two electrolysis units are connected in series. This is sensible if the voltage of the concentrator solar cell at the operating point achieves twice the voltage necessary for the electrolysis, i.e. approx. 3 volts. Such high voltages can be achieved with a single highly efficient cascade solar cell made of III-V semiconductors.
  • FIG. 6 A possible construction for the series connection of two PEM electrolysis units is shown in FIG. 6 . The following meanings apply in this Figure:

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US11/576,939 2004-10-18 2005-10-07 Device and Method for Photovoltaic Generation of Hydrogen Abandoned US20070246370A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102004050638A DE102004050638B3 (de) 2004-10-18 2004-10-18 Vorrichtung und Verfahren zur photovoltaischen Erzeugung von Wasserstoff
DE102004050638.8 2004-10-18
PCT/EP2005/010844 WO2006042650A2 (de) 2004-10-18 2005-10-07 Vorrichtung und verfahren zur photovoltaischen erzeugung von wasserstoff

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EP (1) EP1834012B1 (de)
DE (1) DE102004050638B3 (de)
ES (1) ES2562913T3 (de)
WO (1) WO2006042650A2 (de)

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WO2012044891A2 (en) * 2010-09-30 2012-04-05 University Of Delaware Devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis
WO2013143885A1 (de) * 2012-03-30 2013-10-03 Evonik Industries Ag Photoelektrochemische zelle, system und verfahren zur lichtgetriebenen erzeugung von wasserstoff und sauerstoff mit einer photoelektrochemischen zelle und verfahren zur herstellung der photoelektrochemischen zelle
EP2835449A1 (de) * 2013-08-05 2015-02-11 Badini, Angelo Photovoltaisches Modul zur Herstellung von Wasserstoff
US20160340789A1 (en) * 2015-05-21 2016-11-24 Palo Alto Research Center Incorporated Photoelectrolysis system and method
US20160376712A1 (en) * 2014-03-11 2016-12-29 Kabushiki Kaisha Toshiba Photochemical reaction device
US9593053B1 (en) * 2011-11-14 2017-03-14 Hypersolar, Inc. Photoelectrosynthetically active heterostructures
US9755023B2 (en) 2011-09-30 2017-09-05 The University Of Kentucky Research Foundation Photoelectrochemical cell including Ga(Sbx)N1-x semiconductor electrode
US9751759B2 (en) 2012-10-01 2017-09-05 Oxford University Innovation Limited Composition for hydrogen generation
WO2018033886A1 (en) * 2016-08-19 2018-02-22 Ecole Polytechnique Federale De Lausanne (Epfl) Integrated photo-electrochemical device for concentrated irradiation
US10087535B2 (en) 2015-03-23 2018-10-02 Alliance For Sustainable Energy, Llc Devices and methods for photoelectrochemical water splitting
US10378116B2 (en) * 2014-03-24 2019-08-13 Kabushiki Kaisha Toshiba Photoelectrochemical reaction device
WO2021181149A1 (pt) * 2020-03-10 2021-09-16 Fusion Welcome-Fuel, Unipessoal Lda Dispositivo com acoplamento directo para geração de hidrogénio a partir de luz solar concentrada
US11248301B2 (en) 2016-08-19 2022-02-15 Ecole polytechnique fédérale de Lausanne (EPFL) Integrated photo-electrochemical device for concentrated irradiation
CN114318385A (zh) * 2021-12-30 2022-04-12 苏州光汇新能源科技有限公司 一体式光电化学制氢模组和光电化学制氢系统
US11492713B2 (en) * 2018-08-11 2022-11-08 West Chester University Energy storage system for metal upcycling
FR3127763A1 (fr) * 2021-10-04 2023-04-07 Commissariat A L'energie Atomique Et Aux Energies Alternatives Convertisseur photoélectrochimique pour la production de dihydrogène.

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US8759138B2 (en) 2008-02-11 2014-06-24 Suncore Photovoltaics, Inc. Concentrated photovoltaic system modules using III-V semiconductor solar cells
US9331228B2 (en) 2008-02-11 2016-05-03 Suncore Photovoltaics, Inc. Concentrated photovoltaic system modules using III-V semiconductor solar cells
US8093492B2 (en) 2008-02-11 2012-01-10 Emcore Solar Power, Inc. Solar cell receiver for concentrated photovoltaic system for III-V semiconductor solar cell
US9012771B1 (en) 2009-09-03 2015-04-21 Suncore Photovoltaics, Inc. Solar cell receiver subassembly with a heat shield for use in a concentrating solar system
US9806215B2 (en) 2009-09-03 2017-10-31 Suncore Photovoltaics, Inc. Encapsulated concentrated photovoltaic system subassembly for III-V semiconductor solar cells
DE102012003597A1 (de) 2012-02-23 2013-08-29 Helmholtz-Zentrum Berlin Für Materialien Und Energie Gmbh Photovoltaische Hybrid-Elektrolysezelle

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012044891A3 (en) * 2010-09-30 2012-06-14 University Of Delaware Devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis
WO2012044891A2 (en) * 2010-09-30 2012-04-05 University Of Delaware Devices and methods for increasing solar hydrogen conversion efficiency in photovoltaic electrolysis
US9755023B2 (en) 2011-09-30 2017-09-05 The University Of Kentucky Research Foundation Photoelectrochemical cell including Ga(Sbx)N1-x semiconductor electrode
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WO2013143885A1 (de) * 2012-03-30 2013-10-03 Evonik Industries Ag Photoelektrochemische zelle, system und verfahren zur lichtgetriebenen erzeugung von wasserstoff und sauerstoff mit einer photoelektrochemischen zelle und verfahren zur herstellung der photoelektrochemischen zelle
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