AU2014246142B2 - Gas production apparatus - Google Patents
Gas production apparatus Download PDFInfo
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- AU2014246142B2 AU2014246142B2 AU2014246142A AU2014246142A AU2014246142B2 AU 2014246142 B2 AU2014246142 B2 AU 2014246142B2 AU 2014246142 A AU2014246142 A AU 2014246142A AU 2014246142 A AU2014246142 A AU 2014246142A AU 2014246142 B2 AU2014246142 B2 AU 2014246142B2
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- gas
- hydrogen
- production apparatus
- oxygen
- gas production
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 118
- 239000007789 gas Substances 0.000 claims abstract description 102
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 66
- 239000004065 semiconductor Substances 0.000 claims abstract description 51
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 31
- 239000010409 thin film Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000010408 film Substances 0.000 claims description 135
- 229910052739 hydrogen Inorganic materials 0.000 claims description 82
- 239000001257 hydrogen Substances 0.000 claims description 82
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 47
- 239000001301 oxygen Substances 0.000 claims description 47
- 229910052760 oxygen Inorganic materials 0.000 claims description 47
- 239000008151 electrolyte solution Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000010030 laminating Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 103
- 238000006243 chemical reaction Methods 0.000 description 74
- 238000000034 method Methods 0.000 description 50
- 230000001681 protective effect Effects 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 230000006870 function Effects 0.000 description 25
- 229910052738 indium Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- 229910052733 gallium Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006303 photolysis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- -1 hydroxide ions Chemical class 0.000 description 5
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000224 chemical solution deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001552 radio frequency sputter deposition Methods 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910004613 CdTe Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001786 chalcogen compounds Chemical class 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 229910002451 CoOx Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
-
- 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
- C25B9/73—Assemblies comprising two or more cells of the filter-press type
-
- 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
- H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0687—Multiple junction or tandem solar 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
- H01L31/06—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 characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0725—Multiple junction or tandem solar cells
-
- 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
- Y02E10/544—Solar cells from Group III-V materials
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
This gas production apparatus is provided with: a laminate which is obtained by laminating multiple elements in series, each of the multiple elements bearing semiconductor thin films that form a pn junction therebetween, and which has a light-receiving section on one side and a conductive substrate on the other side; a hydrogen gas production section which is formed on the surface of a first element present on the light-receiving section side; a first electrolysis chamber which includes the hydrogen gas production section; an oxygen gas production section which is formed on the back surface of the conductive substrate; a second electrolysis chamber which includes the oxygen gas production section; and an ion-permeable and gas-impermeable diaphragm provided between the first and second electrolysis chambers.
Description
DESCRIPTION TITLE OF INVENTION: Gas Production Apparatus
TECHNICAL FIELD
[0001]
The present invention relates to a gas production apparatus. Specifically, the present invention relates to a gas production apparatus that produces hydrogen and oxygen by decomposing water by receiving light.
BACKGROUND ART
[0002]
In the prior art, as one of the modes of using solar light energy as a renewable energy, hydrogen production apparatuses have been suggested which produce hydrogen used for fuel cells and the like by using a photoelectric conversion material used for solar cells and utilizing electrons and holes obtained by photoelectric conversion for a decomposition reaction of water (for example, see Patent Literatures 1 and 2).
In both of the hydrogen production apparatuses disclosed in Patent Literatures 1 and 2, a photoelectric conversion portion or a solar cell, in which two or more pn junctions generating an electromotive force when solar light is incident thereon are connected to each other in series, is provided; an electrolytic solution chamber is disposed at the lower side of the photoelectric conversion portion or the solar cell that is opposite to a light receiving surface which receives solar light on the upper side of the photoelectric conversion portion or the solar cell; and the inside of an electrolysis chamber is divided by an ion-conductive partition or diaphragm, and the documents disclose that by the electric power that is generated in the photoelectric conversion portion or the solar cell by the received solar light, water is electrolyzed, and hydrogen is generated.
[0003]
According to Patent Literature 1, because the hydrogen production apparatus can also adjust the orientation of the light receiving surface with respect to the solar light, the amount of incident light that will be subjected to photoelectric conversion can be increased, and hydrogen generation efficiency is not reduced.
Furthermore, according to Patent Literature 2, because the hydrogen production apparatus electrolyzes water by using electrode plates, which are connected to a p-type semiconductor and an n-type semiconductor of the solar cell, as a positive electrode and a negative electrode respectively, the efficiency of conversion of solar energy into hydrogen can be improved.
CITATION LIST PATENT LITERATURE
[0004]
Patent Literature 1: JP 2012-177160 A
Patent Literature 2: JP 2004-197167 A
SUMMARY OF INVENTION
[0005]
In both of the hydrogen production apparatuses disclosed in Patent Literatures 1 and 2, in the electrolysis chamber that is on the side opposite to the light receiving surface of the photoelectric conversion portion or the solar cell, that is, in the electrolysis chamber that is on the back surface side of the photoelectric conversion portion or the solar cell, hydrogen and oxygen are generated as a result of electrolysis of water.
Therefore, if the generated gas such as hydrogen or oxygen adheres to a gas generation surface of the gas generating electrode of the photoelectric conversion portion or the electrode plate of the solar cell and stays between the gas generation surface and an aqueous solution such as an electrolytic solution, a contact area between the gas generation surface and the aqueous solution is reduced, and this leads to a problem in that the efficiency of generating gas such as hydrogen and oxygen is reduced.
Although the hydrogen production apparatuses disclosed in Patent Literatures 1 and 2 show high gas generation efficiency particularly at the initial gas generation stage, with the passage of time, the amount of gas staying between the gas generation surface and the aqueous solution such as an electrolytic solution increases. As a result, because a contact area between the gas generation surface and the aqueous solution is reduced, the efficiency of generating gas such as hydrogen and oxygen greatly decreases, and this leads to a problem in that gas cannot be stably generated.
[0006]
It would be advantageous if at least an embodiment of the present invention were to solve the aforementioned problems of the prior art and to provide a gas production apparatus which can maintain high gas generation efficiency at the initial gas generation stage and even after the passage of time, and can stably produces hydrogen gas and oxygen gas as high-purity gases completely separated from each other.
[0007] A first aspect of the present invention provides a gas production apparatus comprising: an element laminate in which a plurality of elements, each having a light receiving portion and including a semiconductor thin film with pn junction, are so laminated on each other as to connect in series to each other; a hydrogen gas generator which is formed on a surface of a first element among the plurality of elements and generates hydrogen gas, the first element being positioned at one end of the element laminate; a first electrolysis chamber which includes the hydrogen gas generator and contains an aqueous electrolytic solution in contact with the hydrogen gas generator, and the hydrogen gas generated; an oxygen gas generator that is formed on a back surface of a conductive substrate, on which the semiconductor thin film of a second element among the plurality of elements is formed, and generates oxygen gas, the second element being positioned at another end of the element laminate; a second electrolysis chamber which includes the oxygen gas generator and contains an aqueous electrolytic solution in contact with the oxygen gas generator, and the oxygen gas generated; and a diaphragm which is ion-permeable but gas-impermeable, and is provided between the first electrolysis chamber and the second electrolysis chamber, wherein a transparent conductive film and a hydrogen generation promoter are formed on a light receiving surface of the first element.
[0008]
The hydrogen gas generator is preferably provided with a hydrogen generation surface which is formed on a surface of the semiconductor thin film of the first element.
The first element is preferably composed of a plurality of sub-elements which are disposed on the second element discretely with respect to the second element.
Preferably, the plurality of sub-elements each have an element area smaller than that of the second element.
The oxygen gas generator is preferably provided with an oxygen generation surface which is formed on the back surface of the conductive substrate and inclined upward along a flow direction of the aqueous electrolytic solution in the second electrolysis chamber.
[0009]
It is preferable that the semiconductor thin film includes a CIGS-based compound semiconductor.
It is also preferable that the semiconductor thin film includes a CZTS-based compound semiconductor.
Preferably, the semiconductor thin film has an absorption wavelength edge equal to or greater than 800 nm.
The gas production apparatus preferably further comprises a hydrogen generation promoter provided on the hydrogen generation surface of the hydrogen gas generator.
Preferably, the hydrogen generation promoter is platinum. Another aspect of the invention provides gas generated by the gas production apparatus of the first aspect. [0010]
According to an embodiment of the present invention, it may be possible to maintain high gas generation efficiency at the initial gas generation stage and even after the passage of time and to stably produce hydrogen gas and oxygen gas as high-purity gases completely separated from each other. BRIEF DESCRIPTION OF DRAWINGS [0011]
Embodiments will now be described by way of example only with reference to the accompanying non-limiting Figures, in which: [FIG. 1] FIG. 1 is a cross-sectional view schematically showing an example of a gas production apparatus according to an embodiment.
[FIG. 2] FIG. 2 is a top view of the gas production apparatus shown in FIG. 1.
[FIG. 3] FIG. 3 is a flow chart showing an example of a process of manufacturing the gas production apparatus shown in FIG. 1. DESCRIPTION OF EMBODIMENTS [0012]
Hereinafter, the gas production apparatus according to the present invention will be specifically described based on a preferred embodiment shown in the attached drawings.
An embodiment of the present invention is an apparatus producing hydrogen and oxygen by using, as an electrode for decomposing water, a semiconductor thin film having a pn junction and used in a solar cell or the like. With a single element constituted with, for example, a pn junction-semiconductor thin film, a conductive film, and a support substrate, the ability to photolyze water is insufficient, and an electromotive force equal to or higher than a starting voltage of electrolysis of water is not obtained. Therefore, in the apparatus, a plurality of elements are connected to each other in series in order that the electromotive force may be increased, and the total electromotive force of the elements may become equal to or higher than the starting voltage of electrolysis of water. Furthermore, in the apparatus, through a photolysis reaction of water, hydrogen is generated from the side of a light receiving surface of the elements, oxygen is generated from the side of a surface opposite to the light receiving surface, and thus the hydrogen and oxygen generated by the decomposition of water are separately collected. In this way, the apparatus produces hydrogen and oxygen at a high purity. As the method for connecting the elements to each other, a method is preferably used in which the element that will be laminated on an element having a large element area is constituted with a plurality of sub-elements having a small element area, and the sub-elements are discretely laminated on the element having a large element area.
[0013]
First, characteristics of the gas production apparatus according to an embodiment of the invention will be described in comparison with the gas production apparatus of the prior art.
As described above, in the prior art, all of the surfaces (gas generation surfaces) of the electrodes for electrolysis that generate gas are disposed on the back surface side of the photoelectric conversion portion that is opposite to the light receiving surface receiving solar light. In contrast, an embodiment of the present invention is characterized in that the hydrogen generation surface and the light receiving surface receiving solar light are disposed on the same side. In this way, if the hydrogen generation surface is disposed on the side of the light receiving surface, desired effects, such as being able to maintain high gas generation efficiency regardless of the passage of time and being able to stably produce hydrogen gas and oxygen gas, may be obtained.
[0014] FIG. 1 is a cross-sectional view schematically showing an example of a gas production apparatus according to an embodiment of the present invention, and FIG. 2 is a top view of the gas production apparatus shown in FIG. 1.
First, as shown in the drawings, a gas production apparatus 10 has an element laminate 12 in which a plurality of elements, in each of which a semiconductor thin film having a pn junction is formed, are vertically laminated on each other in series; a hydrogen gas generation portion 14a which is disposed at an open end of the element positioned at the upper end of the element laminate 12; an oxygen gas generation portion 14b which is disposed at an open end of the element positioned at the lower end of the element laminate 12; a container 18 constituting an electrolysis chamber 16 which contains an aqueous electrolytic solution AQ in contact with the two gas generation portions 14a and 14b, and hydrogen gas and oxygen gas that are generated in the gas generation portions 14a and 14b respectively; and a diaphragm 20 which partitions the electrolysis chamber 16 into two electrolysis chambers 16a and 16b including the gas generation portions 14a and 14b respectively.
[0015]
The element laminate 12 is for generating hydrogen and oxygen through a photolysis reaction of water by receiving light such as solar light through a light receiving surface, and has a plurality of (two in the example illustrated in the drawings) pn junction elements 22 and 24 that are vertically laminated on each other in the drawing. Hereinafter, as a typical example, the number of the pn junction elements connected to each other in series is described as two. However, as long as the total electromotive force of a plurality of pn junction elements is equal to or higher than the starting voltage of the electrolysis of water, the number of the pn junction elements is not limited to two as in the example illustrated in the drawings. It goes without saying that the number of the pn junction elements may be arbitrarily set.
The pn junction elements 22 and 24 are photoelectric conversion elements with a laminated structure having the same constitution as that of a solar battery cell used as a solar cell. The pn junction elements 22 and 24 are for generating electrons and holes through photoelectric conversion by receiving light such as solar light through the light receiving surfaces, and sending the generated electrons and holes to the gas generation portions 14a and 14b respectively.
[0016]
The pn junction element 22 on the substrate side of the element laminate 12, that is, on the lower side in the drawing is an oxygen generation element generating oxygen and has a conductive plate 26, a photoelectric conversion layer 28, and a buffer layer 30 that are laminated on each other in this order from the lower side toward the upper side in the drawing. The pn junction element 22 has a transparent conductive film 32, which becomes an upper electrode, on the buffer layer 30.
The pn junction element 24 on the light receiving surface side of the element laminate 12, that is, on the upper side in the drawing is a hydrogen generation element generating hydrogen. The pn junction element 24 is an assembly of a plurality of (nine in the example illustrated in the drawings) small-sized pn junction elements 24a. The nine small-sized pn junction elements (hereafter also referred to as "sub-elements") 24a are disposed on the pn junction element 22, specifically, on the transparent conductive film 32 discretely, that is, in the form of scattered islands. In the pn junction element 24 (24a), the transparent conductive film 32, the photoelectric conversion layer 28, the buffer layer 30, and a transparent protective film 34 are laminated on each other in this order from the pn junction element 22 on the lower side toward the upper side in the drawing. On the transparent protective film 34, a promoter 36 for generating hydrogen is formed in the form of scattered islands .
[0017]
The transparent conductive film 32 functions as a lower electrode in the pn junction element 24 (24a) and functions as an upper electrode in the pn junction element 22. Therefore, it can be said that the transparent conductive film 32 functions as an electrode common to both the pn junction elements 22 and 24 (24a) . Since the transparent protective film 34 constitutes an upper electrode of the pn junction element 24 (24a), a transparent conductive protective film is used as the transparent protective film 34.
Accordingly, it can be said that the pn junction element 24 (24a) is constituted with the transparent conductive film 32, the photoelectric conversion layer 28, the buffer layer 30, the transparent protective film 34, and the hydrogen generation promoter 36.
Incidentally, the sub-elements 24a are discretely disposed in the form of scattered islands on the transparent conductive film 32, so that, in a position in which the sub-elements 24a are not disposed, the transparent conductive film 32 is so exposed in the electrolysis chamber 16a as to come into contact with the aqueous electrolytic solution AQ to thereby short-circuit. Furthermore, the lateral faces of the pn junction element 24 (24a), that is, the lateral faces of the photoelectric conversion layer 28, the buffer layer 30 and the transparent protective film 34 as laminated are also exposed in the electrolysis chamber 16a and comes into contact with the aqueous electrolytic solution AQ, and therefore a short circuit occurs .
Accordingly, it is preferable to cover the surface of the transparent conductive film 32 in portions exposed in the electrolysis chamber 16a, and the lateral faces of the pn junction element 24 (24a) as well, with a transparent insulating film 37.
[0018]
In the element laminate 12, light is incident on the pn junction element 24 from the transparent protective film 34 side and passes through the transparent protective film 34 and the buffer layer 30. As a result, an electromotive force is generated in the photoelectric conversion layer 28, and for example, the migration of a charge (electrons) to the transparent protective film 34 from the transparent conductive film 32 occurs. In other words, an electric current flowing to the transparent conductive film 32 from the transparent protective film 34 is generated (the migration of holes occurs).
On the other hand, light incident on the pn junction element 22 from the transparent insulating film 37 side passes through the transparent insulating film 37, the transparent conductive film 32, and the buffer layer 30. As a result, an electromotive force is generated in the photoelectric conversion layer 28, and for example, the migration of a charge (electrons) to the transparent conductive film 32 from the conductive plate 26 occurs. In other words, an electric current flowing to the conductive plate 26 from the transparent conductive film 32 is generated (the migration of holes occurs).
Therefore, in the element laminate 12, the transparent protective film 34 of the pn junction element 24 on the upper side becomes the gas generation portion 14a (cathode electrode for electrolysis) generating hydrogen, and the conductive plate 26 of the pn junction element 22 on the lower side becomes the gas generation portion 14b (anode electrode for electrolysis) generating oxygen.
[0019]
The conductive plate 26 is composed of, for example, Mo, and functions as a substrate supporting the element laminate 12 and as an oxygen generation surface generating oxygen.
The photoelectric conversion layer 28 is composed of, for example, a CIGS-based compound semiconductor film or a CZTS-based compound semiconductor film. In the pn junction element 22 on the lower side, the photoelectric conversion layer 28 is formed on the conductive plate 26, and in the pn junction element 24 on the upper side, the photoelectric conversion layer 28 is formed on the transparent conductive film 32.
The buffer layer 30 is composed of, for example, a CdS thin film and is formed on the surface of the photoelectric conversion layer 28. At the interface between the buffer layer 30 and the photoelectric conversion layer 28, pn junction is formed. Consequently, it can be said that the photoelectric conversion layer 28 is a thin film of a p-type semiconductor, and the buffer layer 30 is a thin film of an n-type semiconductor .
The photoelectric conversion layer 28 and the buffer layer 30 are used in both the pn junction element 22 on the lower side and the pn junction element 24 on the upper side, and at least one of the photoelectric conversion layer 28 and the buffer layer 30 may be the same for both the pn junction elements 22 and 24 or may vary between the pn junction elements 22 and 24.
[0020]
The transparent conductive film 32 is composed of, for example, a transparent conductive film such as an IMO (Mo-added In2C>3) film and is formed on the buffer layer 30. Herein, in the pn junction element 22 on the lower side, the transparent conductive film 32 functions as an upper electrode. Accordingly, the transparent conductive film 32 is a conductive film which functions as a light receiving surface on the pn junction composed of the buffer layer 30 and the photoelectric conversion layer 28 in the pn junction element 22, and also functions as a lower electrode of the pn junction element 24 on the upper side. That is, the transparent conductive film 32 functions as a conductive film which connects the pn junction element 22 on the lower side to the pn junction element 24 on the upper side in series .
The transparent protective film 34 is composed of, for example, a transparent conductive film such as an ITO (Sn-added ln203) film, and is formed on the buffer layer 30 in the pn junction element 24 on the upper side. Herein, the transparent protective film 34 functions as an upper electrode of the pn junction element 24 on the upper side. Accordingly, the transparent protective film 34 functions as the light receiving surface on the pn junction composed of the buffer layer 30 and the photoelectric conversion layer 28 and also functions as the hydrogen generation surface generating hydrogen.
[0021]
The conductive plate 26 is constituted with, for example, a metal such as Mo, Al, Cu, Cr, W, Ni, Ta, Fe or Co, or a combination of these metals. The conductive plate 26 may have a single layer structure or a laminated structure such as a double layer structure. The back surface of the conductive plate 26 becomes an oxygen gas generation surface generating oxygen and comes into direct contact with an aqueous electrolytic solution. Therefore, the conductive plate 26 is preferably of a metal that is not easily oxidized. Particularly, the conductive plate 26 is preferably constituted with Mo. The film thickness of the conductive plate 26 is generally about 1,000 μιη, and preferably 100 μπι to 1,500 μπι.
[0022]
The back surface of the conductive plate 26 of the pn junction element 22 becomes the gas generation portion 14b (anode electrode for electrolysis) generating oxygen, and generates oxygen molecules, that is, oxygen (oxygen gas) by withdrawing electrons from hydroxide ions OH” ionized from water molecules in the aqueous electrolytic solution AQ (20H’ —> H20 + 02/2 + 2e”) , that is to say, functions as an oxygen gas generation surface.
Accordingly, the back surface of the conductive plate 26 is preferably inclined toward the downstream side from the upstream side along the stream of the aqueous electrolytic solution AQ such that the generated oxygen does not stay on the back surface. The direction of the inclination is not particularly limited. When the back surface of the conductive plate 26 is inclined downward toward the downstream side, the oxygen generated on the back surface is highly effectively removed.
When it is inclined upward toward the downstream side, it is possible to cause the oxygen gas, which floats from the aqueous electrolytic solution AQ and is concentrated on the back surface of the conductive plate 26, to flow to a discharge port 40b together with the aqueous electrolytic solution AQ with efficiency. In the example as illustrated, a supply port 38b of the aqueous electrolytic solution AQ is on the right side in the drawing, and the discharge port 40b for discharging the generated oxygen together with the aqueous electrolytic solution AQ is on the left side in the drawing. Consequently, in order to rapidly discharge the generated oxygen, it is better for the back surface of the conductive plate 26 to be inclined upward toward the left side in the drawing from the right side in the drawing.
[0023]
If the back surface of the conductive plate 26 is inclined as above, it is possible to rapidly move the generated oxygen from the back surface of the conductive plate 26 that serves as the oxygen generation surface, without causing the oxygen to stay on the back surface, and to discharge the oxygen from the discharge port 40b together with the aqueous electrolytic solution AQ. Therefore, it is possible to bring the back surface of the conductive plate 26 into contact with the aqueous electrolytic solution AQ at all times, and to generate oxygen with excellent efficiency by causing a photolysis reaction of water on the entire back surface of the conductive plate 26.
In order to accelerate the generation of oxygen by the photolysis reaction of water, an oxygen generation promoter such as Ir02, CoOx or the like may be formed in the form of scattered islands on the back surface of the conductive plate 26 which becomes the oxygen gas generation surface.
[0024]
At the interface between the buffer layer 30 and the photoelectric conversion layer 28, the photoelectric conversion layer 28 forms the pn junction of which the photoelectric conversion layer 28 side is of a P-type and the buffer layer 30 side is of an N-type. The photoelectric conversion layer 28 absorbs the light reaching it after passing through the transparent insulating film 37, the transparent conductive film 32 and the buffer layer 30, generates holes on the p-side and electrons on the n-side, and has a function of photoelectric conversion. In the photoelectric conversion layer 28, the holes generated in the pn junction are migrated toward the conductive plate 26 from the photoelectric conversion layer 28, and the electrons generated in the pn junction are migrated toward the transparent conductive film 32 from the buffer layer 30. The film thickness of the photoelectric conversion layer 28 is preferably 200 nm to 3,000 nm, and particularly preferably 500 nm to 2,000 nm.
[0025]
The photoelectric conversion layer 28 is preferably a compound semiconductor-based photoelectric conversion semiconductor layer. The main component of the photoelectric conversion layer 28 is not particularly limited (the main component referring to a component comprising not less than 20% by weight of the layer) . In view of obtaining high photoelectric conversion efficiency, a chalcogen compound semiconductor, a compound semiconductor having a chalcopyrite structure, and a compound semiconductor having a defect stannite-type structure can be suitably used as the main component.
Favorable examples of the chalcogen compound (compound containing S, Se, or Te) include: a II-VI compound such as ZnS, ZnSe, ZnTe, CdS, CdSe or
CdTe; a group I-III-VI2 compound such as CuInSe2, CuGaSe2, Cu(In, Ga)Se2, CuInS2, CuGaSe2 or Cu(In, Ga) (S, Se)2; and a group I-III3-VI5 compound such as Culn3Se5, CuGa3Ses or Cu(In, Ga)3Ses.
[0026]
Favorable examples of the compound semiconductors of a chalcopyrite-type structure and of a defect stannite-type structure include: a group I-III-VI2 compound such as CuInSe2, CuGaSe2, Cu(In, Ga)Se2, CuInS2, CuGaSe2 or Cu(In, Ga) (S, Se)2; and a group I-III3-VI5 compound such as CuIn3Ses, CuGa3Ses or Cu (In, Ga)3Ses.
In the above description, (In, Ga) and (S, Se) represent (In!-xGax) and (Si-ySey) respectively (here, x = 0 to 1, y = 0 to 1) .
[0027]
The photoelectric conversion layer 28 is preferably constituted with, for example, a CIGS-based compound semiconductor having a chalcopyrite crystal structure or a CZTS-based compound semiconductor, among others. That is, the photoelectric conversion layer 28 is preferably constituted with a CIGS layer. The CIGS layer may be constituted not only with Cu(In, Ga)Se2 but also with a known material used in the CIGS-based material such as CuInSe2(CIS) .
The method for forming the photoelectric conversion layer 28 is not particularly limited. For example, as the method for forming the CIGS layer containing Cu, In, Ga, or S, 1) a multisource vapor deposition method, 2) a selenization method, 3) a sputtering method, 4) a hybrid sputtering method, and 5) a mechanochemical processing method are known.
Examples of other methods for forming the CIGS layer include a screen printing method, a close-spaced sublimation method, an MOCVD method, a spraying method (wet film formation method), and the like. For example, by a screen printing method (wet film formation method), a spraying method (wet film formation method) or the like, a fine particle film containing elements of group lb, group Illb, and group VIb is formed on a substrate and subjected to thermal decomposition processing (optionally performed in a group VIb element atmosphere), and in this way, a crystal having a desired composition can be obtained (JP 9-74065 A, JP 9-74213 A, and the like).
[0028]
As described above, in the present invention, the photoelectric conversion layer 28 is preferably constituted with a CIGS-based compound semiconductor having a chalcopyrite crystal structure or a CZTS-based compound semiconductor, for example. However, the present invention is not limited thereto, and any photoelectric conversion element may be used as long as it makes it possible to form a pn junction composed of an inorganic semiconductor and generate hydrogen and oxygen by causing a photolysis reaction of water. For example, a photoelectric conversion element utilized in a solar battery cell constituting a solar battery is preferably used. Examples of such a photoelectric conversion element include a thin film silicon-based thin film-type photoelectric conversion element, a CdTe-based thin film-type photoelectric conversion element, a dye-sensitized thin film-type photoelectric conversion element, and an organic thin film-type photoelectric conversion element, in addition to a CIGS-based thin film-type photoelectric conversion element, a CIS-based thin film-type photoelectric conversion element, and a CZTS-based thin film-type photoelectric conversion element.
The absorption wavelength of the inorganic semiconductor forming the photoelectric conversion layer 28 is not particularly limited as long as the absorption wavelength is within a wavelength range allowing photoelectric conversion. The wavelength range may be any range including wavelength regions of solar light and the like, particularly, from a visible wavelength region to an infrared wavelength region. The absorption wavelength edge of the inorganic semiconductor is preferably equal to or greater than 800 nm, that is to say, a wavelength range including up to an infrared wavelength region is preferred. This is because more than half of the solar light energy reaching the ground is included in an ultraviolet-visible region at wavelengths of not more than 800 nm, and effective use of such solar energy makes it significant to produce hydrogen energy by the inventive apparatus as an alternative to fossil fuels .
[0029]
The buffer layer 30 is so formed as to constitute a pn junction layer together with the photoelectric conversion layer 28, that is, to form a pn junction at the interface between the photoelectric conversion layer 28 and the buffer layer 30, to protect the photoelectric conversion layer 28 at the time of forming the transparent conductive film 32, and to transmit the light incident on the transparent conductive film 32 to the photoelectric conversion layer 28.
The buffer layer 30 preferably contains a metal sulfide containing at least one metal element selected from the group consisting of Cd, Zn, Sn and In, with specific examples including CdS, ZnS, Zn(S, 0) and/or Zn(S, 0, OH), SnS, Sn(S, 0) and/or Sn(S, 0, OH), InS, In(S, 0) and/or In(S, 0, OH). The film thickness of the buffer layer 30 is preferably 10 nm to 2 μιη, and more preferably 15 nm to 200 nm. The buffer layer 30 is formed by, for example, a chemical bath deposition process (hereafter referred to as "CBD process"). A window layer may be disposed between the buffer layer 30 and the transparent conductive film 32. The window layer is constituted with, for example, a ZnO layer having a thickness of about 10 nm.
[0030]
The transparent conductive film 32 has light transmitting properties. In the pn junction element 22 on the lower side, the transparent conductive film 32 brings light into the photoelectric conversion layer 28, and functions as an upper electrode that is paired with the conductive plate 26 as a lower electrode and moves the holes and electrons generated in the photoelectric conversion layer 28 (to causes an electric current to flow). Furthermore, the transparent conductive film 32 functions as a lower electrode of the pn junction element 24 on the upper side and also functions as a transparent conductive film for directly connecting the pn junction element 22 on the lower side to the pn junction element 24 on the upper side such that the pn junction elements 22 and 24 are connected to each other in series.
The transparent conductive film 32 is constituted with IMO (Mo-added I^Ct) , ZnO doped with Al, B, Ga, In or the like, or ITO (indium tin oxide), for example. The transparent conductive film 32 may have a single layer structure or a laminated structure such as a double layer structure. The thickness of the transparent conductive film 32 is not particularly limited, and is preferably 0.1 μιη to 2 μιη, and more preferably 0.3 μιη to 1 μιη.
The method for forming the transparent conductive film 32 is not particularly limited. The transparent conductive film can be formed by a vapor phase film formation method such as an electron beam vapor deposition method, a sputtering method and a CVD method or by a coating method.
[0031]
The transparent protective film 34 is formed on the upper surface of the buffer layer 30 in the pn junction element 24 on the upper side and has light transmitting properties. The transparent protective film 34 brings light into the photoelectric conversion layer 28, functions as an upper electrode that is paired with the transparent conductive film 32 as a lower electrode and moves the holes and electrons generated in the photoelectric conversion layer 28 (to causes an electric current to flow), and functions as a transparent conductive film which protects the buffer layer 30 and the photoelectric conversion layer 28.
In addition, the transparent protective film 34 serves as the gas generation portion 14a (cathode electrode for electrolysis) generating hydrogen and generates hydrogen molecules, that is, hydrogen (hydrogen gas) by supplying electrons to hydrogen ions (protons) H+ ionized from water molecules (2H+ + 2e“ —> H2) . The surface of the transparent protective film 34 functions as a hydrogen gas generation surface .
As the transparent protective film 34, it is possible to use the same transparent conductive film as the transparent conductive film 32, such as ITO (indium tin oxide), ZnO doped with Al, B, Ga, In or the like, or IMO (Mo-added In2C>3) . The transparent protective film 34 may have a single layer structure or a laminated structure such as a double layer structure, as the transparent conductive film 32. The thickness of the transparent protective film 34 is not particularly limited, and is preferably 10 nm to 200 nm, and more preferably 30 nm to 100 nm.
The method for forming the transparent protective film 34 is not particularly limited, as is the case with the transparent conductive film 32. The transparent protective film 34 can be formed by a vapor phase film formation method such as an electron beam vapor deposition method, a sputtering method and a CVD method or by a coating method.
[0032]
As described above, the transparent protective film 34 functions as an electrode for generating hydrogen, and the surface thereof functions as a hydrogen gas generation surface. Accordingly, the transparent protective film 34 functions as the gas generation portion 14a generating hydrogen, and the region thereof constitutes a hydrogen gas generation region.
On the surface of the transparent protective film 34, the hydrogen generation promoter 36 for accelerating the generation of hydrogen is formed in the form of scattered islands.
Examples of the hydrogen generation promoter 36 include a component composed solely of Pt (platinum), Pd (palladium), Ni (nickel), Au (gold), Ag (silver), Ru (ruthenium), Cu (copper),
Co (cobalt), Rh (rhodium), Ir (iridium), or Mn (manganese), an alloy as a combination of these, and an oxide thereof. The size of the hydrogen generation promoter 36 is not particularly limited, and is preferably 1 nm to 100 nm.
The method for forming the hydrogen generation promoter 36 is not particularly limited, and the hydrogen generation promoter 36 can be formed by a photodeposition method, a sputtering method, an impregnation method, or the like.
[0033]
As in the example illustrated, it is preferable that the hydrogen generation promoter 36 is provided on the upper surface of the transparent protective film 34. However, when hydrogen can be sufficiently generated, the hydrogen generation promoter 36 may be not provided.
In the example illustrated, the hydrogen generation promoter 36 is formed and scattered on the upper surface of the transparent protective film 34 formed on the upper surface of the buffer layer 30. However, the present invention is not limited thereto. The transparent protective film 34 may not be provided, and the hydrogen generation promoter 36 may be directly formed and scattered on the upper surface of the buffer layer 30.
In this case, the buffer layer 30 functions as an N-type semiconductor and as an electrode for generating hydrogen, and the surface thereof functions as a hydrogen gas generation surface. Therefore, the buffer layer 30 functions as the gas generation portion 14a generating hydrogen, and the region thereof constitutes a hydrogen gas generation region.
[0034]
The transparent insulating film 37 has light transmitting properties. For protecting the pn junction elements 22 and 24, specifically, for protecting the portion outside the hydrogen gas generation regions in the electrolysis chamber 16a, the transparent insulating film 37 is so provided as to cover the portion outside the gas generation regions. Specifically, the transparent insulating film 37 covers the portion of the surface of the transparent conductive film 32 that does not have the pn junction element 24 on the upper side formed therein and, accordingly, serves as the light receiving surface of the pn junction element 22 on the lower side, and all the lateral faces of the individual sub-elements 24a constituting the pn junction element 24.
The transparent insulating film 37 is constituted with, for example, Si02, Sn02, Nb205, Ta20s, A1203, Ga2C>3 or the like. The thickness of the transparent insulating film 37 is not particularly limited, and is preferably 100 nm to 1,000 nm.
The method for forming the transparent insulating film 37 is not particularly limited. The transparent insulating film 37 can be formed by an RF sputtering method, a DC reactive sputtering method, an MOCVD method or the like.
[0035]
The region of the transparent conductive film 32, in which the transparent insulating film 37 is formed while the pn junction element 24 on the upper side is not formed, serves as the light receiving surface of the pn junction element 22 on the lower side. In contrast, in each of the sub-elements 24a of the pn junction element 24 on the upper side, the buffer layer 30 or the transparent protective film 34 of the relevant sub-element serves as the light receiving surface. Consequently, in order to generate hydrogen and oxygen with excellent efficiency by a photolysis reaction of water, according to the ability of the pn junction elements 22 and 24, for example, according to the electromotive force or the amount of electrons or holes generated, a predetermined balance needs to be achieved between the total light receiving area of the pn junction element 24 on the upper side, that is, the total area of the light receiving surfaces of all the sub-elements 24a, and the total light receiving area of the pn junction element 22 on the lower side, that is, the total area of the region of the transparent conductive film 32 in which the pn junction element 24 on the upper side is not formed. For example, when the pn junction elements 22 and 24 are equal in ability, they are preferably also equal in total light receiving area.
Therefore, it is preferable that the total light receiving areas of the pn junction elements 22 and 24 are balanced according to their ability.
The element laminate 12 is constituted as above.
[0036]
The element laminate 12 can be manufactured by the following manufacturing method, but the present invention is not limited thereto. FIG. 3 is a flowchart showing an example of a process of manufacturing the gas production apparatus shown in FIGS. 1 and 2 .
First, in Step S100, as the conductive plate 26, for example, a Mo substrate is prepared.
Thereafter, in Step S102, on one surface of the conductive plate 26, as the photoelectric conversion layer 28, for example, a CIGS-based compound semiconductor film (P-type semiconductor layer) is formed by a known method such as a selenization/sulfuration method or a multi-source simultaneous vapor deposition method.
Then, in Step S104, on the photoelectric conversion layer 28 formed as above, as the buffer layer 30, for example, a CdS film (N-type semiconductor layer) is formed by a known method such as a CBD (chemical bath deposition) process.
Subsequently, in Step S106, on the buffer layer 30 formed as above, as the transparent conductive film 32, for example, an ITO film which becomes a transparent conductive layer is formed by a known method such as an MOCVD method or an RF sputtering method.
[0037]
Thereafter, in Step S108, on the transparent conductive film 32 formed as above, as the photoelectric conversion layer 28, for example, a CIGS-based compound semiconductor film (P-type semiconductor layer) is formed in the same manner as in Step S102.
Then, in Step S110, on the photoelectric conversion layer 28 formed as above, as the buffer layer 30, for example, a CdS film (N-type semiconductor layer) is formed in the same manner as in Step S104.
Subsequently, in Step S112, on the buffer layer 30 formed as above, as the transparent protective film 34, for example, a ZnO film which becomes a protective layer is formed by a known method such as an MOCVD method or an RF sputtering method.
After that, in Step S114, a structure A (pn junction element 24 on the upper side) composed of the photoelectric conversion layer 28 (CIGS-based compound semiconductor film), the buffer layer 30 (CdS film), and the transparent protective film 34 (ZnO film) formed as above is cut by a mechanical scribing method, thereby forming a group of structures A (a group of sub-elements 24a) that are discretely disposed.
[0038]
Then, in Step S116, on the group of structures A formed as above, as the transparent insulating film 37, for example, a Si02 film which becomes a transparent insulating layer is formed by a known method such as an MOCVD method, an RF sputtering method, or a DC reactive sputtering method. Subsequently, by a known method such as a CMP method, the transparent insulating film 37 (Si02 film) formed on the upper surface portion of the structures A is selectively scraped off such that the transparent protective film 34 (ZnO film), which becomes a protective layer, is exposed only on the upper surface portion of the sub-elements 24a (structures A) as the pn junction element 24.
Finally, in Step S118, only on the transparent protective film 34 exposed on the upper surface portion of the pn junction element 24 (sub-elements 24a) (structures A), as the hydrogen generation promoter 36, for example, a Pt promoter is supported by a known method such as a photodeposition method.
In this way, the element laminate 12 can be manufactured.
[0039]
The container 18 houses the element laminate 12 and constitutes the electrolysis chamber 16 composed of the electrolysis chamber 16a on the upper side, which contains (retains) the aqueous electrolytic solution AQ in contact with the upper surface of the transparent protective film 34 of the pn junction element 24a on the upper side constituting the gas generation portion 14a, contains (retains) hydrogen as the gas generated from the gas generation portion 14a, and is provided on the upper side of the element laminate 12, and the electrolysis chamber 16b on the lower side, which contains (retains) the aqueous electrolytic solution AQ in contact with the back surface of the conductive plate 26 of the pn junction element 22 at the lower end constituting the gas generation portion 14b, contains (retains) oxygen as the gas generated from the gas generation portion 14b, and is provided on the lower side of the element laminate 12.
As shown in FIG. 2, the electrolysis chamber 16a on the upper side and the electrolysis chamber 16b on the lower side communicate with each other in a region that surrounds the outer periphery of the element laminate 12 along the inner surface of the container 18, and a diaphragm 20 is disposed in the region in which the electrolysis chambers 16a and 16b communicate with each other.
[0040] A plurality of (three in the example illustrated in the drawings) supply ports 38a for supplying the aqueous electrolytic solution AQ into the electrolysis chamber 16a are provided in an upper part of a lateral face on the right side in FIG. 1 of the electrolysis chamber 16a in the container 18 (on the upper right side of the apparatus). Furthermore, a plurality of (four in the example illustrated in the drawings) discharge ports 40a for discharging the aqueous electrolytic solution AQ in the electrolysis chamber 16a and a plurality of (three in the example illustrated in the drawings) collection ports 42 for collecting hydrogen generated in the electrolysis chamber 16a are both provided in an upper part of a lateral face on the left side in FIG. 1 of the electrolysis chamber 16a in the container 18 (on the upper left side of the apparatus). A plurality of (two in the example illustrated in the drawings) supply ports 38b for supplying the aqueous electrolytic solution AQ into the electrolysis chamber 16b are provided in a lower part of a lateral face on the right side in FIG. 1 of the electrolysis chamber 16b in the container 18 (on the lower right side of the apparatus). Furthermore, a plurality of (two in the example illustrated in the drawings) discharge ports 40b for discharging the aqueous electrolytic solution AQ in the electrolysis chamber 16b together with oxygen generated in the electrolysis chamber 16b are provided in a lower part of a lateral face on the left side in FIG. 1 of the electrolysis chamber 16b in the container 18 (on the lower left side of the apparatus). The oxygen discharged from the discharge ports 40b together with the aqueous electrolytic solution AQ is collected by a collection portion not shown in the drawings.
[0041]
Both the supply ports 38a and the discharge ports 40a are provided in a position slightly above the position of the transparent protective film 34, such that a water flow, which prevents the hydrogen generated by the transparent protective film 34 of the pn junction element 24 (a group of the subelements 24a) from staying on the surface of the transparent protective film 34, can be generated in the electrolysis chamber 16a. Therefore, it is possible to bring the surface of the transparent protective film 34 into contact with the aqueous electrolytic solution AQ at all times, and to generate hydrogen with excellent efficiency. It goes without saying that the position of the supply ports 38a and the discharge ports 40a is the same as the position of the surface of the aqueous electrolytic solution AQ in the electrolysis chamber 16a.
In contrast, both the supply ports 38b and the discharge ports 40b are placed in the position of the back surface of the conductive plate 26 that constitutes the ceiling of the electrolysis chamber 16b and is inclined upward toward the downstream side.
In the electrolysis chamber 16a, hydrogen is retained above the surface of the aqueous electrolytic solution AQ. Therefore, the ceiling of the electrolysis chamber 16a is constituted such that it is inclined upward toward the downstream side, as the back surface of the conductive plate 26, and is separated from the surface of the aqueous electrolytic solution AQ.
Furthermore, in order to collect the retained hydrogen with excellent efficiency, the collection ports 42 are provided in a position slightly above the position of the surface of the aqueous electrolytic solution AQ, that is, a position slightly above the position of the supply ports 38a and the discharge ports 40a.
[0042]
The number of the supply port 38a, the discharge port 40a, and the collection port 42 is not particularly limited, and may be arbitrarily set as long as a water flow, which prevents the hydrogen from staying on the hydrogen gas generation surface, can be generated. However, it is preferable to provide a required number of the supply ports 38a, the discharge ports 40a, and the collection ports 42 in a position ensuring a water flow on the surface of the pn junction element 24 (a group of the sub-elements 24a).
The number of the supply ports 38b and the discharge ports 40b is not particularly limited either, and may be arbitrarily set as long as a water flow, which prevents the oxygen from staying on the oxygen gas generation surface, can be generated. However, it is preferable to provide a required number of the supply ports 38b and the discharge ports 40b in a position ensuring a water flow on the back surface of the conductive plate 26 of the pn junction element 22.
[0043]
In order that the hydrogen generated in the electrolysis chamber 16a and the oxygen generated in the electrolysis chamber 16b may be separately collected at high purity, and that the hydroxide ions increased as a result of the generation of hydrogen in the electrolysis chamber 16a (with increased pH) and the hydrogen ions increased as a result of the generation of oxygen in the electrolysis chamber 16b (with reduced pH) may permeate the diaphragm 20 to cause neutralization, the diaphragm 20 separates the electrolysis chamber 16 in the container 18 into the electrolysis chamber 16a and the electrolysis chamber 16b. The diaphragm 20 is a membrane permeable to ions but impermeable to gas.
As described above, the diaphragm 20 is disposed in a region surrounding the outer periphery of the element laminate 12 along the inner surface of the container 18, in which region the electrolysis chamber 16a on the upper side and the electrolysis chamber 16b on the lower side communicate with each other. The diaphragm 20 is attached to the inner wall surface of the container 18 and the outer wall surface of the element laminate 12 in a state of coming into close contact with these without a void. As a result, the diaphragm 20 can separate the region of the electrolysis chamber 16a, which comes into contact with the pn junction element 24 on the upper side, from the region of the electrolysis chamber 16b, which comes into contact with the pn junction element 22, such that the permeation of gas does not occur while the permeation of ions occur.
The diaphragm 20 is constituted with, for example, an ion exchange membrane, a ceramic filter, or Vycor glass. The thickness of the diaphragm 20 is not particularly limited, and is preferably 10 μπι to 1,000 μιη.
The gas production apparatus of the present invention is basically constituted as above.
[0044]
The gas production apparatus of the present invention has been specifically described, but the present invention is not limited to the aforementioned examples. It goes without saying that the present invention can be improved or modified in various ways without departing from the gist and scope of the present invention.
EXAMPLES
[0045]
Hereinafter, the gas production apparatus of embodiments of the present invention will be specifically described based on the following Examples, to which the present invention is not limited. (Example 1)
First, as Example 1, the gas production apparatus 10 shown in FIG. 1 that was constituted as below was prepared, the electrolysis chamber 16 was filled with an aqueous electrolytic solution, the apparatus was irradiated with light, and the amount of the generated hydrogen gas and oxygen gas was evaluated.
The results are shown in Table 1.
The element laminate 12 of the gas production apparatus 10 of Example 1 was prepared according to the preparation flow shown in the flowchart of FIG. 3.
[0046] 1. Constitution of hydrogen generation element (pn junction element 24 (sub-elements 24a)).
Transparent conductive film: IMO (Mo-added In203) , a thickness of 1,000 nm P-type semiconductor thin film: CIGS, a thickness of 500 nm N-type semiconductor thin film: CdS, a thickness of 50 nm Protective film: ITO (Sn-added In2C>3) , a thickness of 50 nm Promoter: Pt 2. Constitution of oxygen generation element (pn junction element 22).
Conductive plate: Mo, a thickness of 1 mm P-type semiconductor thin film: CIGS, a thickness of 2,000 nm N-type semiconductor thin film: CdS, a thickness of 50 nm 3. Form of conductive plate.
Shape on oxygen gas generation side: processed to be inclined toward the flow direction of oxygen gas (no oxygen gas bubbles staying) 4. Form of oxygen generation element.
Size: 15 cm x 20 cm 5. Form of hydrogen generation element.
Size: 3 cm to 5 cm for each side Number of elements: nine (two or more)
Disposition of elements: the respective elements are discretely disposed. 6. Others
Diaphragm: Nafion (substance permeable to ions but impermeable to gas)
Aqueous electrolytic solution: 0.1 M Na2S04 solution (pH 9.5)
Promoter: Pt particles (size: up to 20 nm in diameter) Material for container (module): glass
Light source for irradiation: irradiation with simulated solar light of AM 1.5.
[0047] (Comparative Example 1)
As Comparative Example 1, a gas production apparatus of the same constitution as that of Example 1 was prepared except that the hydrogen generation portion and the oxygen generation portion were formed in the same element. The prepared gas production apparatus was irradiated with light in the same manner as in Example 1, and the amount of the generated gas was evaluated.
The results are shown in Table 1.
[0048] (Comparative Example 2)
Next, as Comparative Example 2, a gas production apparatus of the same constitution as that of Example 1 was prepared except that the hydrogen generation element and the oxygen generation element have the same size (15 cm x 20 cm), and the apparatus was constituted with one hydrogen generation element and one oxygen generation element. The prepared gas production apparatus was irradiated with light in the same manner as in Example 1, and the amount of the generated gas was evaluated.
The results are shown in Table 1.
[0049]
The evaluation was performed as below.
As the amount of gas generated (initial stage), the amount of gas generated immediately after the start of light irradiation was measured.
As the amount of gas generated (after a passage of time), the amount of gas generated 24 hours after the start of light irradiation was measured.
In Table 1, "A" of the column of comprehensive determination indicates a case in which both the amount of hydrogen gas generated (initial stage) and the amount of hydrogen gas generated (after a passage of time) exceeded 50 ml/min-m2, while "B" of the column of comprehensive determination indicates a case in which either or both of the amount of hydrogen gas generated (initial stage) and the amount of hydrogen gas generated (after a passage of time) were less than 50 ml/min'm2. Based on such determination criteria, the evaluation was made. Herein, the standard value of 50 ml/min^m2 is a numerical value converted based on a solar light conversion efficiency of 1%.
[0050] [Table 1]
[0051]
As shown in Table 1, in Example 1 of the present invention, the amount of hydrogen gas generated immediately after the start of light irradiation was 65 ml/min-m2, and the amount of hydrogen gas generated after 24 hours was 55 ml/min-m2. Because the generated hydrogen gas bubbles adhered to part of the hydrogen generation portion on the light receiving surface side, the contact area between the hydrogen generation portion and the solution was reduced due to the bubbles, and as a result, the gas generation efficiency was reduced, and the amount of gas generated after 24 hours was reduced compared to the initial stage. However, by discretely disposing the hydrogen generation elements, a turbulent flow occurred in the water introduced into the apparatus, and in this way, most of the bubbles could be removed.
[0052]
In Comparative Example 1, the amount of hydrogen gas generated immediately after the start of light irradiation was 0 ml/min'm2, and the generation of gas could not be detected. Furthermore, the amount of hydrogen gas generated was still 0 ml/min'm2 even after 24 hours, and the generation of gas could not be detected.
In Comparative Example 2, the amount of hydrogen gas generated immediately after the start of light irradiation was 55 ml/min-m2. Because the element for generating hydrogen gas covered the entirety of the element for generating oxygen gas, the amount of light reaching the element for generating oxygen gas was reduced, and accordingly, the total gas generation ability of the system was reduced. Furthermore, the amount of hydrogen gas generated after 24 hours was 30 ml/min'm2. Because the generated hydrogen gas bubbles covered the entire light receiving surface, light was scattered due to the bubbles, and accordingly, the amount of incident light was reduced, and the gas generation efficiency was markedly reduced.
[0053]
As is evident from the above results, in Example 1, a large amount of gas was generated immediately after the start of light irradiation, and the amount of gas generated could be maintained at a high level even after a passage of time. Therefore, it is understood that gas could be stably generated.
In contrast, it is understood that, in Comparative Example 1, a potential (electromotive force) necessary for decomposing water into hydrogen and oxygen could not be obtained.
Moreover, it is understood that, in Comparative Example 2, although a large amount of gas was generated immediately after the start of light irradiation, the amount of gas generated was markedly reduced after a passage of time, and gas could not be stably generated. The above results show the superiority of Example 1.
The above results clearly show the effects of an embodiment of the present invention.
REFERENCE SIGNS LIST
[0054]
10: GAS PRODUCTION APPARATUS
12: ELEMENT LAMINATE
14a, 14b: GAS GENERATION PORTION
16, 16a, 16b: ELECTROLYSIS CHAMBER
18: CONTAINER
20: DIAPHRAGM
22, 24, 24a: PN JUNCTION ELEMENT
26: CONDUCTIVE PLATE
28: PHOTOELECTRIC CONVERSION LAYER
30: BUFFER LAYER
32: TRANSPARENT CONDUCTIVE FILM
34: TRANSPARENT PROTECTIVE FILM
36: PROMOTER
37: TRANSPARENT INSULATING FILM
[ 0055]
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word ''comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
Claims (11)
- CLAIMS [Claim 1] A gas production apparatus, comprising: an element laminate in which a plurality of elements, each having a light receiving portion and including a semiconductor thin film with pn junction, are so laminated on each other as to connect in series to each other; a hydrogen gas generator which is formed on a surface of a first element among the plurality of elements and generates hydrogen gas, the first element being positioned at one end of the element laminate; a first electrolysis chamber which includes the hydrogen gas generator and contains an aqueous electrolytic solution in contact with the hydrogen gas generator, and the hydrogen gas generated; an oxygen gas generator that is formed on a back surface of a conductive substrate, on which the semiconductor thin film of a second element among the plurality of elements is formed, and generates oxygen gas, the second element being positioned at another end of the element laminate; a second electrolysis chamber which includes the oxygen gas generator and contains an aqueous electrolytic solution in contact with the oxygen gas generator, and the oxygen gas generated; and a diaphragm which is ion-permeable but gas-impermeable, and is provided between the first electrolysis chamber and the second electrolysis chamber, wherein a transparent conductive film and a hydrogen generation promoter are formed on a light receiving surface of the first element. [Claim
- 2] The gas production apparatus according to claim 1, wherein the hydrogen gas generator is provided with a hydrogen generation surface, and the hydrogen generation surface is formed on a surface of the semiconductor thin film of the first element. [Claim
- 3] The gas production apparatus according to claim 1 or 2, wherein the first element is composed of a plurality of subelements, and the plurality of sub-elements are disposed on the second element discretely with respect to the second element. [Claim
- 4] The gas production apparatus according to claim 3, wherein the plurality of sub-elements each have an element area smaller than that of the second element. [Claim
- 5] The gas production apparatus according to any one of claims 1 to 4, wherein: the oxygen gas generator is provided with an oxygen generation surface formed on the back surface of the conductive substrate; and the oxygen generation surface is inclined upward along a flow direction of the aqueous electrolytic solution in the second electrolysis chamber. [Claim
- 6] The gas production apparatus according to any one of claims 1 to 5, wherein the semiconductor thin film includes a CIGS-based compound semiconductor. [Claim
- 7] The gas production apparatus according to any one of claims 1 to 5, wherein the semiconductor thin film includes a CZTS-based compound semiconductor. [Claim
- 8] The gas production apparatus according to any one of claims 1 to 7, wherein the semiconductor thin film has an absorption wavelength edge equal to or greater than 800 nm. [Claim
- 9] The gas production apparatus according to any one of claims 1 to 8, wherein the hydrogen generation promoter is provided on the hydrogen generation surface of the hydrogen gas generator. [Claim
- 10] The gas production apparatus according to any one of claims 1 to 9, wherein the hydrogen generation promoter is platinum. [Claim
- 11] Gas generated by the gas production apparatus according to any one of claims 1 to 10.
Applications Claiming Priority (3)
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| JP2013-068993 | 2013-03-28 | ||
| JP2013068993A JP5993768B2 (en) | 2013-03-28 | 2013-03-28 | Gas production equipment |
| PCT/JP2014/057583 WO2014156899A1 (en) | 2013-03-28 | 2014-03-19 | Gas production apparatus |
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| AU2014246142A1 AU2014246142A1 (en) | 2015-10-22 |
| AU2014246142B2 true AU2014246142B2 (en) | 2016-06-23 |
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| US (1) | US20160017506A1 (en) |
| JP (1) | JP5993768B2 (en) |
| CN (1) | CN105102683B (en) |
| AU (1) | AU2014246142B2 (en) |
| WO (1) | WO2014156899A1 (en) |
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| JP6184312B2 (en) * | 2013-12-13 | 2017-08-23 | 富士フイルム株式会社 | Artificial photosynthetic array |
| JP6239733B2 (en) | 2014-03-24 | 2017-11-29 | 株式会社東芝 | Photoelectrochemical cell, method for producing photoelectrochemical cell, and photoelectrochemical reaction apparatus |
| JP6258124B2 (en) * | 2014-05-20 | 2018-01-10 | 株式会社東芝 | Photoelectrochemical reactor |
| JP6412417B2 (en) * | 2014-11-27 | 2018-10-24 | 富士フイルム株式会社 | Hydrogen generating electrode and manufacturing method thereof |
| JP2016104897A (en) * | 2014-12-01 | 2016-06-09 | 株式会社東芝 | Photoelectrode, method of manufacturing the same, and photoelectrochemical reactor using the same |
| WO2016114063A1 (en) * | 2015-01-13 | 2016-07-21 | 富士フイルム株式会社 | Hydrogen generating electrode |
| JPWO2017110217A1 (en) * | 2015-12-22 | 2018-09-13 | 富士フイルム株式会社 | Photocatalytic electrode and artificial photosynthesis module |
| CN105441972B (en) * | 2015-12-28 | 2018-08-10 | 深圳市赫拉铂氢时代科技有限公司 | Cavity-separating hydrogen-oxygen detaches electrolysis unit and its method |
| KR101984408B1 (en) * | 2017-11-30 | 2019-05-30 | 전남대학교산학협력단 | Cathode for Water Electrolysis and Manufacturing Method Thereof |
| WO2019172014A1 (en) * | 2018-03-06 | 2019-09-12 | 富士フイルム株式会社 | Photocatalytic electrode for electrolysis and electrolysis device |
| CN108922927B (en) * | 2018-06-21 | 2020-07-14 | 华南师范大学 | Stable compound semiconductor sunlight decomposition water hydrogen production electronic device, electrode system and preparation method thereof |
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| US7052587B2 (en) * | 2003-06-27 | 2006-05-30 | General Motors Corporation | Photoelectrochemical device and electrode |
| KR20090052696A (en) * | 2007-11-21 | 2009-05-26 | 한국전자통신연구원 | Dye-sensitized solar cells having substrate including p-n junction diode |
| JPWO2010010956A1 (en) * | 2008-07-25 | 2012-01-05 | 株式会社アルバック | Thin-film solar cell manufacturing apparatus and manufacturing method, and thin-film solar cell |
| JP4761327B2 (en) * | 2010-01-12 | 2011-08-31 | シャープ株式会社 | Wet solar cell and wet solar cell module |
| JP5663254B2 (en) * | 2010-02-08 | 2015-02-04 | シャープ株式会社 | Hydrogen production apparatus and hydrogen production method |
| JP5802374B2 (en) * | 2010-05-19 | 2015-10-28 | シャープ株式会社 | Solar cell integrated gas production system |
| TWI559472B (en) * | 2010-07-02 | 2016-11-21 | ３Ｍ新設資產公司 | Barrier assembly with encapsulant and photovoltaic cell |
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| JP5118233B2 (en) * | 2011-06-08 | 2013-01-16 | シャープ株式会社 | Photoelectric conversion element and photoelectric conversion element module |
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| JP2014189883A (en) | 2014-10-06 |
| AU2014246142A1 (en) | 2015-10-22 |
| WO2014156899A1 (en) | 2014-10-02 |
| CN105102683B (en) | 2017-08-25 |
| CN105102683A (en) | 2015-11-25 |
| JP5993768B2 (en) | 2016-09-14 |
| US20160017506A1 (en) | 2016-01-21 |
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