CN116445949A - Photovoltaic hydrogen production device and preparation method thereof - Google Patents
Photovoltaic hydrogen production device and preparation method thereof Download PDFInfo
- Publication number
- CN116445949A CN116445949A CN202310350054.XA CN202310350054A CN116445949A CN 116445949 A CN116445949 A CN 116445949A CN 202310350054 A CN202310350054 A CN 202310350054A CN 116445949 A CN116445949 A CN 116445949A
- Authority
- CN
- China
- Prior art keywords
- hydrogen production
- type semiconductor
- semiconductor film
- heavily doped
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 176
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 176
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 157
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 4
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- 238000003475 lamination Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 230000005641 tunneling Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002070 nanowire Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 5
- 238000004549 pulsed laser deposition Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 perovskite Chemical compound 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000012546 transfer Methods 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
- 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
-
- 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
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic System characterised by the doping material
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035227—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
-
- 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
Abstract
The invention discloses a photovoltaic hydrogen production device and a preparation method thereof, wherein the device comprises a hydrogen production module, a first electrode and a second electrode; the hydrogen production module comprises a plurality of hydrogen production units which are arranged in a lamination way; each hydrogen production unit comprises a heavily doped n-type semiconductor substrate, an n-type semiconductor film, an intrinsic semiconductor film, a p-type semiconductor film and a heavily doped p-type semiconductor film which are sequentially stacked from bottom to top; the first electrode is connected with a heavily doped p-type semiconductor film of the uppermost hydrogen production unit of the hydrogen production module; the second electrode is connected with the heavily doped n-type semiconductor substrate of the hydrogen production unit at the lowest layer of the hydrogen production module. The hydrogen production module is formed by connecting a plurality of semiconductor homogeneous pn junctions in series, can obtain the potential of high enough hydrogen cracking, can separate out hydrogen and oxygen at the cathode and the anode respectively, has high light energy utilization rate, high photovoltaic hydrogen production efficiency and low cost, does not have a catalyst, uses water as a reactant, is economical and environment-friendly, and can realize industrial large-scale hydrogen production.
Description
Technical Field
The invention discloses a photovoltaic hydrogen production device and a preparation method thereof, and belongs to the technical field of hydrogen production equipment.
Background
Hydrogen is an ideal secondary energy source, and depending on the mass, any other fuel releases less energy during combustion than hydrogen, for example: CH (CH) 4 The heat value per unit mass of gasoline and coal are predicted to be respectively higher than H 2 2.4, 2.8 and 4 times lower. Hydrogen fuel cells have been applied to a small amount in the automotive field at present, and with the continued research of this industry, they will be widely used in future human life.
48% of commercial hydrogen comes from the cracking of fossil fuels, 30% of hydrogen produced by alcohol cracking, 18% of hydrogen produced by coke oven gas, and 4% from water. The hydrogen is prepared by taking water as the raw material, so that the hydrogen is cleaner and the raw material is cheap and easy to obtain. The main modes for preparing hydrogen by taking water as a raw material in the prior art comprise water electrolysis hydrogen preparation and photocatalytic water hydrogen preparation. For hydrogen production by electrolysis of water, alkaline electrolysis of water is the cheapest way of hydrogen production by electrolysis at the present stage, but the energy utilization efficiency is not ideal. Proton exchange membrane (Proton Exchange Membrane, PEM) water electrolysis hydrogen production technology is currently not amenable to large scale use due to durability and cost issues of its electrolyzer. The main principle of the photocatalysis water hydrogen production method is that light irradiates the catalyst to generate induction effect, because the energy of the light is larger than the width of the forbidden band of the catalyst, electrons in the valence band are transited to the conduction band to generate charges, holes are generated in the valence band, the charges participate in reduction reaction to generate hydrogen, and the holes participate in oxidation reaction to generate oxygen. In the prior art, the photocatalytic water hydrogen production mainly absorbs ultraviolet light in sunlight, but the ultraviolet light in the sunlight only accounts for 3 percent, the energy utilization rate is low, and in the method for producing the photocatalytic water hydrogen, light is easy to refract and absorb in the process of passing through a primary energy concentrator, a reactor and a reaction solution, solar energy cannot be fully utilized, and light energy loss can be caused; at the interface with slower catalysis, the aggregation of excitation charges is easy to occur, the serious electron recombination problem occurs, and the generation efficiency of hydrogen is reduced, so that the hydrogen production cost is higher, and the industrial large-scale hydrogen production is difficult to realize.
Disclosure of Invention
The purpose of the application is to provide a photovoltaic hydrogen production device and a preparation method thereof, so as to solve the technical problems that the hydrogen production cost is high and the industrial large-scale hydrogen production is difficult to realize in the prior art of photocatalytic water hydrogen production.
A first aspect of the present invention provides a photovoltaic hydrogen production apparatus comprising a hydrogen production module, a first electrode, and a second electrode;
the hydrogen production module comprises a plurality of hydrogen production units which are arranged in a stacked manner;
each hydrogen production unit comprises a heavily doped n-type semiconductor substrate, an n-type semiconductor film, an intrinsic semiconductor film, a p-type semiconductor film and a heavily doped p-type semiconductor film which are sequentially stacked from bottom to top;
the first electrode is connected with a heavily doped p-type semiconductor film of the uppermost hydrogen production unit of the hydrogen production module;
and the second electrode is connected with the heavily doped n-type semiconductor substrate of the hydrogen production unit at the lowest layer of the hydrogen production module.
Preferably, the number of the hydrogen production modules is a plurality;
the plurality of hydrogen production modules are arranged in an array;
the first electrode is connected with the heavily doped p-type semiconductor film of the uppermost hydrogen production unit of each hydrogen production module;
the second electrode is connected with the heavily doped n-type semiconductor substrate of the hydrogen production unit at the lowest layer of each hydrogen production module.
Preferably, the heavily doped n-type semiconductor substrate has a doping concentration of 10 19 -10 21 cm -3 ；
The doping concentration of the n-type semiconductor film is 10 12 -10 18 cm -3 ；
The doping concentration of the heavily doped p-type semiconductor film is 10 18 -10 20 cm -3 ；
The doping concentration of the p-type semiconductor film is 10 12 -10 17 cm -3 。
Preferably, the thickness of the n-type semiconductor film and the heavily doped n-type semiconductor substrate is 100-300nm;
the thickness of the intrinsic semiconductor film is 50-150nm;
the thickness of the p-type semiconductor film and the heavily doped p-type semiconductor film is 100-300nm.
Preferably, the semiconductor used in the heavily doped n-type semiconductor substrate, the n-type semiconductor film, the intrinsic semiconductor film, the p-type semiconductor film, and the heavily doped p-type semiconductor film is the same as that used in the heavily doped p-type semiconductor film, and is silicon, perovskite, copper indium compound, or cadmium telluride.
Preferably, the first electrode is a gold electrode or a cobalt electrode, and the second electrode is a platinum electrode or an iridium electrode.
Preferably, the heavily doped n-type semiconductor substrate is a rigid substrate.
Preferably, the number of hydrogen production units is greater than or equal to 40.
The second aspect of the invention provides a method for preparing a photovoltaic hydrogen plant, comprising:
the hydrogen production unit is obtained by sequentially stacking a heavily doped n-type semiconductor substrate, an n-type semiconductor film, an intrinsic semiconductor film, a p-type semiconductor film and a heavily doped p-type semiconductor film from bottom to top;
stacking a plurality of hydrogen production units to obtain a hydrogen production module;
and connecting the first electrode with a heavily doped p-type semiconductor film of the uppermost hydrogen production unit of the hydrogen production module, and connecting the second electrode with a heavily doped n-type semiconductor substrate of the lowermost hydrogen production unit of the hydrogen production module to obtain the photovoltaic hydrogen production device.
Compared with the prior art, the photovoltaic hydrogen production device and the preparation method thereof have the following advantages that
The beneficial effects are that:
the photovoltaic hydrogen production device and the preparation method thereof have the advantages of high light energy utilization rate, high photovoltaic hydrogen production efficiency, low cost, no catalyst, and economy and environmental protection, and can realize industrial large-scale hydrogen production by using water as a reactant.
Drawings
FIG. 1 is a schematic diagram of a hydrogen production unit in accordance with an embodiment of the present invention;
FIG. 2 is a diagram of a 4 row and 2 column silicon nanowire array in accordance with an embodiment of the present invention;
fig. 3 is a schematic diagram of the use of the 4 row 2 column silicon nanowire array of fig. 2.
101 is a heavily doped p-type semiconductor film; 102 is a p-type semiconductor film; 103 is an intrinsic semiconductor film; 104 is an n-type semiconductor film; 105 is a heavily doped n-type semiconductor substrate; 201 is a second electrode; 202 is a semiconductor substrate; 203 is the first electrode.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, techniques, etc., in order to provide a thorough understanding of the embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
The photocatalytic water hydrogen production in the prior art has the following technical problems: (1) loss of light energy: in the photocatalysis process, light is easy to refract and absorb in the process of passing through a primary energy concentrator, a reactor and a reaction solution, solar energy cannot be fully utilized, and only ultraviolet light is responded; (2) charge recombination, i.e. electron pair recombination: at the interface with slower catalysis, aggregation of excitation charges is easy to occur, serious electron recombination problem occurs, and the generation efficiency of hydrogen is reduced; (3) In heterogeneous catalytic environmental reactions, mass flow barrier caused by reactant and product transfer: molecules and ions flow from a large amount of fluid to a photocatalytic reaction site, and undergo diffusion, hydrogen and oxygen are generated on the surface of a catalyst after electrons are received, and the gas gradually forms to cause slow interfacial catalytic reaction, so that serious reverse reaction is caused, serious energy loss is generated, and the generation of hydrogen is not facilitated; (4) The efficiency of a catalyst is primarily affected by its bandgap and the type of light it receives, and the sensitivity of the catalyst depends on its bandgap energy for water decomposition, while the reduction and oxidation potentials must be maintained within the bandgap of the catalyst to effect a photocatalytic reaction.
In order to solve the above problems, the present invention provides a photovoltaic hydrogen production apparatus, comprising a hydrogen production module, a first electrode 203 and a second electrode 201;
the hydrogen production module comprises a plurality of hydrogen production units which are arranged in a stacked mode;
the structure of each hydrogen production unit is as shown in fig. 1, and comprises a heavily doped n-type semiconductor substrate 105, an n-type semiconductor film 104, an intrinsic semiconductor film 103, a p-type semiconductor film 102 and a heavily doped p-type semiconductor film 101 which are sequentially stacked from bottom to top; the heavily doped n-type semiconductor substrate 105, the n-type semiconductor film 104, the intrinsic semiconductor film 103, the p-type semiconductor film 102, and the heavily doped p-type semiconductor film 101 are the same as each other, and are silicon, perovskite materials, copper indium compounds (specifically, cuInGaSe), cadmium telluride, or the like;
the first electrode 203 is connected with the heavily doped p-type semiconductor film 101 of the uppermost hydrogen production unit of the hydrogen production module;
the second electrode 201 is connected to the heavily doped n-type semiconductor substrate 105 of the lowermost hydrogen production unit of the hydrogen production module.
The semiconductor used in the invention is silicon, perovskite material, copper indium compound (specifically CuInGaSe) or cadmium telluride, etc., the band gap of the semiconductor material is relatively small, and after infrared light with the wave band of 900-1200nm in solar spectrum is irradiated on the semiconductor material, higher photovoltaic can be formed, thereby meeting the electric potential requirement of electrolyzed water to generate hydrogen.
The invention adopts the semiconductor homogeneous pn junction, utilizes the 900-1200nm wave band of sunlight, utilizes the 1050nm wave band of solar spectrum at the highest efficiency, and has high light energy utilization rate.
The hydrogen production module is formed by connecting a plurality of semiconductor homogeneous pn junctions in series, and can obtain the potential of high enough hydrogen cracking, so that hydrogen and oxygen are separated out from two electrodes of a cathode and an anode respectively. The two sides of each hydrogen production unit are provided with the heavily doped n-type semiconductor substrate and the heavily doped p-type semiconductor film, so that the pn junction between the adjacent hydrogen production units is a tunneling structure, higher tunneling current can be obtained, the problem that the pn junction is reversely biased and nonconductive can be solved, and the efficiency of photovoltaic hydrogen production can be improved.
The photovoltaic hydrogen production device has the advantages of high light energy utilization rate, high photovoltaic hydrogen production efficiency, low cost, no catalyst, economy and environmental protection, and can realize industrial large-scale hydrogen production.
In the embodiment of the invention, in order to further improve the hydrogen production efficiency, the number of the adopted hydrogen production modules is a plurality of;
the plurality of hydrogen production modules are arranged in an array;
the first electrode 203 is connected with the heavily doped p-type semiconductor film 101 of the uppermost hydrogen production unit of each hydrogen production module;
the second electrode 201 is connected to the heavily doped n-type semiconductor substrate 105 of the lowermost hydrogen production unit of each hydrogen production module.
In order to ensure the connection stability, a semiconductor substrate 202 is further arranged between the second electrode 201 and the heavily doped n-type semiconductor substrate 105 of the last hydrogen production unit of each hydrogen production module, and the material of the semiconductor substrate 202 is the same as that of the semiconductor used in the hydrogen production unit.
By way of example, fig. 2 is a diagram of a 4 х 2 (4 rows and 2 columns) silicon nanowire array that can achieve a high density pn junction array that increases the reaction rate of hydrogen production. In FIG. 2, only 4 rows and 2 columns are shown, and the structure can be actually constructed into m rows and n columns (m >2, n > 2), and in theory, a nanowire array of (j/56-1) x (k/56-1) can be photoetched on a substrate of j cm x k cm according to photoetching precision 28 nm.
Further, the heavily doped n-type semiconductor substrate 105 has a doping concentration of 10 19 -10 21 cm -3 ；
The doping concentration of the n-type semiconductor film 104 is 10 12 -10 18 cm -3 ；
The heavily doped p-type semiconductor film 101 has a doping concentration of 10 18 -10 20 cm -3 ；
The doping concentration of the p-type semiconductor film 102 is 10 12 -10 17 cm -3 。
The elements doped in the heavily doped n-type semiconductor substrate 105 and the n-type semiconductor film 104 are pentavalent elements such as phosphorus, arsenic, etc., and the elements doped in the heavily doped p-type semiconductor film 101 and the p-type semiconductor film 102 are trivalent elements such as boron, gallium, etc.
Further, the thickness of the n-type semiconductor film 104 and the heavily doped n-type semiconductor substrate 105 is 100-300nm, for example: 100nm, 150nm, 200nm, 250nm, 300nm, etc.;
the thickness of the intrinsic semiconductor film 103 is 50 to 150nm, for example, 50nm, 80nm, 100nm, 120nm, 150nm, etc.;
the thicknesses of the p-type semiconductor film 102 and the heavily doped p-type semiconductor film 101 are each 100 to 300nm, for example: 100nm, 150nm, 200nm, 250nm, 300nm, etc.
The semiconductor film or the semiconductor substrate with the doping concentration and the thickness ensures that the pn junction between the adjacent hydrogen production units is of a tunneling junction structure, thereby obtaining higher tunneling current, greatly improving the efficiency of photovoltaic hydrogen production, and supplementing the doping concentration and the thickness.
In the embodiment of the present invention, the first electrode 203 is a gold electrode or a cobalt electrode, and the second electrode 201 is a platinum electrode or an iridium electrode. The electrode made of the material is not easy to cause chemical reaction, and is favorable for generating hydrogen.
The heavily doped n-type semiconductor substrate 105 in the embodiment of the present invention is a rigid substrate or a flexible substrate, which is preferably used because it is convenient to prepare and can ensure the stability of the whole photovoltaic hydrogen production apparatus.
To obtain a sufficiently high photovoltaic voltage to electrolyze water, the number of hydrogen production units of embodiments of the present invention is greater than or equal to 40, such that the photovoltaic voltage is greater than 10V.
The reaction of the n-type semiconductor terminal of the invention is: 2H (H) + +2e - →H 2 ↑；
The p-type semiconductor terminal reaction is: 2H (H) 2 O+4h + →O 2 ↑+4H + 。
The semiconductor-based homogeneous pn junction can efficiently absorb 800-1200 nm wavelength in sunlight, is intrinsic absorption for 1050nm wavelength, and fully utilizes the band gap of a semiconductor and the solar spectrum of the band. Because a plurality of pn junctions are connected in series, higher photovoltaic generation voltage can be formed, the potential requirement of electrolytic water can be met, hydrogen ions are gathered to a cathode to perform reduction reaction for hydrogen evolution, and oxygen ions are subjected to oxidation reaction for oxygen evolution at an anode. Gas collecting devices are arranged on two sides of the electrode to collect the produced gas, as shown in figure 3.
When in use, the photovoltaic hydrogen production device is placed in a container filled with water (the photovoltaic hydrogen production device is immersed in electrodes on two sides), gas collecting pipes are arranged on two sides of the electrodes, and the following reaction occurs under the irradiation of sunlight:
2H 2 O+4h + →O 2 ↑+4H + ，2H + +2e - →H 2 ↑
the left collecting pipe collects oxygen and the right collecting pipe collects hydrogen.
The second aspect of the invention provides a preparation method of a photovoltaic hydrogen production device, which specifically comprises the following steps:
a heavily doped n-type semiconductor substrate 105, an n-type semiconductor film 104, an intrinsic semiconductor film 103, a p-type semiconductor film 102 and a heavily doped p-type semiconductor film 101 are sequentially stacked from bottom to top to obtain a hydrogen production unit;
stacking a plurality of hydrogen production units together to obtain a hydrogen production module;
the first electrode 203 is connected with the heavily doped p-type semiconductor film 101 of the uppermost hydrogen production unit of the hydrogen production module, and the second electrode 201 is connected with the heavily doped n-type semiconductor substrate 105 of the lowermost hydrogen production unit of the hydrogen production module, so as to obtain the photovoltaic hydrogen production device.
Wherein, the process for preparing a hydrogen production unit is as follows:
an n-type semiconductor film 104, an intrinsic semiconductor film 103, a p-type semiconductor film 102, and a heavily doped p-type semiconductor film 101 are sequentially deposited or sputtered on a heavily doped n-type semiconductor substrate 105 by means of MOCVD, PLD, or magnetron sputtering. The method comprises the following steps:
depositing or sputtering an n-type semiconductor film 104 on the upper surface of the heavily doped n-type semiconductor substrate 105 by adopting a MOCVD, PLD or magnetron sputtering method, wherein the thickness of the n-type semiconductor film 104 is 100-300nm;
depositing or sputtering an intrinsic semiconductor film 103 on the upper surface of the n-type semiconductor film 104 by adopting a MOCVD, PLD or magnetron sputtering method, wherein the thickness of the intrinsic semiconductor film 103 is 50-150nm;
depositing or sputtering a p-type semiconductor film 102 on the upper surface of the intrinsic semiconductor film 103 by adopting a MOCVD, PLD or magnetron sputtering method, wherein the thickness of the p-type semiconductor film 102 is 100-300nm;
the heavily doped p-type semiconductor film 101 is deposited or sputtered on the upper surface of the p-type semiconductor film 102 by MOCVD, PLD or magnetron sputtering, and the thickness of the heavily doped p-type semiconductor film 101 is 100-300nm.
The method for preparing the hydrogen production module is as follows:
repeating the steps for a plurality of times, and preparing the hydrogen production module with a cylindrical structure or a cuboid structure by adopting a mask photoetching method.
Finally, the upper surface of the heavily doped p-type semiconductor film 101 of the uppermost hydrogen production unit in the hydrogen production module is plated with a first electrode 203 film layer, and the lower surface of the heavily doped n-type semiconductor substrate 105 of the lowermost hydrogen production unit in the hydrogen production module is plated with a second electrode 201 film layer, so that the photovoltaic hydrogen production device can be obtained.
If the silicon nanowire array shown in fig. 2 is to be prepared, a plurality of hydrogen production modules are prepared according to the method, and then the hydrogen production modules are arranged in an array; then, the first electrode 203 is connected with the upper surface of the heavily doped p-type semiconductor film 101 of the uppermost hydrogen production unit of each hydrogen production module; the second electrode 201 is connected to the lower surface of the heavily doped n-type semiconductor substrate 105 of the lowermost hydrogen production unit of each hydrogen production module, and a silicon nanowire array can be obtained.
The present invention is not limited to the above-described preparation method, and the silicon nanowire array shown in fig. 2 may be grown by a gold catalytic vapor-liquid-solid (VLS) process, by way of example; the silicon nanowire array shown in the figure 2 can also be prepared by an electrostatic spinning method, the pn junction region obtained by the method has more defects, and the generation efficiency of electrons and holes is lower; the silicon nanowire array shown in fig. 2 can also be prepared by various methods such as electrospray.
The invention adopts the semiconductor homogeneous pn junction, utilizes the 900-1200nm wave band of sunlight, and utilizes the 1050nm wave band of solar spectrum at the highest efficiency. This is determined by the band gap of the semiconductor, and the near infrared band is largely utilized. By adopting the series connection based on a plurality of semiconductor homogeneous pn junctions, the potential of the hydrogen can be obtained with high enough cracking, so that hydrogen and oxygen can be separated out from the two electrodes of the cathode and the anode respectively. The tunneling junction solves the problem that the pn junction is reversely biased and not conductive by adopting the tunneling design among a plurality of pn junctions, and high tunneling current can be obtained by heavy doping at two sides of the pn junction. The invention comprises: no catalyst, water is used as a reactant, and the method is economical and environment-friendly; the key component design for hydrogen production is as follows: the pn junctions of the semiconductors are connected in series to improve the potential, the problem that the pn junctions are reversely biased and nonconductive is solved by adopting a tunneling junction design between the junctions, the tunneling current of the tunneling junction is improved by adopting a heavy doping design, and the efficiency of photovoltaic hydrogen production can be improved.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (9)
1. The photovoltaic hydrogen production device is characterized by comprising a hydrogen production module, a first electrode and a second electrode;
the hydrogen production module comprises a plurality of hydrogen production units which are arranged in a stacked manner;
each hydrogen production unit comprises a heavily doped n-type semiconductor substrate, an n-type semiconductor film, an intrinsic semiconductor film, a p-type semiconductor film and a heavily doped p-type semiconductor film which are sequentially stacked from bottom to top;
the first electrode is connected with a heavily doped p-type semiconductor film of the uppermost hydrogen production unit of the hydrogen production module;
and the second electrode is connected with the heavily doped n-type semiconductor substrate of the hydrogen production unit at the lowest layer of the hydrogen production module.
2. The photovoltaic hydrogen plant of claim 1, wherein the number of hydrogen modules is a plurality;
the plurality of hydrogen production modules are arranged in an array;
the first electrode is connected with the heavily doped p-type semiconductor film of the uppermost hydrogen production unit of each hydrogen production module;
the second electrode is connected with the heavily doped n-type semiconductor substrate of the hydrogen production unit at the lowest layer of each hydrogen production module.
3. The photovoltaic hydrogen plant of claim 1, wherein the heavily doped n-type semiconductor substrate has a doping concentration of 10 19 -10 21 cm -3 ；
The doping concentration of the n-type semiconductor film is 10 12 -10 18 cm -3 ；
The doping concentration of the heavily doped p-type semiconductor film is 10 18 -10 20 cm -3 ；
The doping concentration of the p-type semiconductor film is 10 12 -10 17 cm -3 。
4. A photovoltaic hydrogen plant according to any of claims 1-3, wherein the thickness of the n-type semiconductor film and the heavily doped n-type semiconductor substrate are each 100-300nm;
the thickness of the intrinsic semiconductor film is 50-150nm;
the thickness of the p-type semiconductor film and the heavily doped p-type semiconductor film is 100-300nm.
5. A photovoltaic hydrogen plant according to any of claims 1-3, characterized in that the semiconductor used in the heavily doped n-type semiconductor substrate, n-type semiconductor film, intrinsic semiconductor film, p-type semiconductor film and heavily doped p-type semiconductor film is the same as that used in the heavily doped n-type semiconductor film, and is silicon, perovskite, copper indium compound or cadmium telluride.
6. A photovoltaic hydrogen plant according to any of claims 1 to 3 wherein the first electrode is a gold or cobalt electrode and the second electrode is a platinum or iridium electrode.
7. A photovoltaic hydrogen plant according to any of claims 1 to 3, wherein the heavily doped n-type semiconductor substrate is a rigid substrate.
8. A photovoltaic hydrogen plant according to any of claims 1 to 3, wherein the number of hydrogen producing units is greater than or equal to 40.
9. A method for preparing a photovoltaic hydrogen plant, comprising:
the heavily doped n-type semiconductor substrate, the n-type semiconductor film, the intrinsic semiconductor film, the p-type semiconductor film and the heavily doped p-type semiconductor film are sequentially stacked from bottom to top to obtain a hydrogen production unit;
stacking a plurality of hydrogen production units to obtain a hydrogen production module;
and connecting the first electrode with a heavily doped p-type semiconductor film of the uppermost hydrogen production unit of the hydrogen production module, and connecting the second electrode with a heavily doped n-type semiconductor substrate of the lowermost hydrogen production unit of the hydrogen production module to obtain the photovoltaic hydrogen production device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310350054.XA CN116445949A (en) | 2023-04-04 | 2023-04-04 | Photovoltaic hydrogen production device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310350054.XA CN116445949A (en) | 2023-04-04 | 2023-04-04 | Photovoltaic hydrogen production device and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116445949A true CN116445949A (en) | 2023-07-18 |
Family
ID=87129599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310350054.XA Pending CN116445949A (en) | 2023-04-04 | 2023-04-04 | Photovoltaic hydrogen production device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116445949A (en) |
-
2023
- 2023-04-04 CN CN202310350054.XA patent/CN116445949A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11349039B2 (en) | Axially-integrated epitaxially-grown tandem wire arrays | |
| EP2535442B1 (en) | Hydrogen production apparatus and method for producing hydrogen | |
| US8632663B2 (en) | Hydrogen production device and method for producing hydrogen | |
| US20180219115A1 (en) | Semiconductor structures for fuel generation | |
| US10242806B2 (en) | Solar fuels generator | |
| DE10393792T5 (en) | Integrated photoelectrochemical cell and system with a liquid electrolyte | |
| WO2013143885A1 (en) | Photoelectrochemical cell, system and process for light-driven production of hydrogen and oxygen with a photoelectrochemical cell, and process for producing the photoelectrochemical cell | |
| US9540741B2 (en) | Light-driven hydroiodic acid splitting from semiconductive fuel generator | |
| US20130174896A1 (en) | Tandem solar cell using a silicon microwire array and amorphous silicon photovoltaic layer | |
| US9476129B2 (en) | Solar fuels generator | |
| Li et al. | Recent progress in hydrogen: From solar to solar cell | |
| US20080314435A1 (en) | Nano engineered photo electrode for photoelectrochemical, photovoltaic and sensor applications | |
| JP5719576B2 (en) | Gas production apparatus and gas production method | |
| CN116445949A (en) | Photovoltaic hydrogen production device and preparation method thereof | |
| WO2013011843A1 (en) | Electrolytic cell, gas producing device, and gas producing method | |
| Pham et al. | Photovoltaic partner selection for high-efficiency photovoltaic-electrolytic water splitting systems: brief review and perspective | |
| Gil et al. | Silicon and tungsten oxide nanostructures for water splitting | |
| Wang et al. | Photoelectrochemical and Photovoltaic–Electrochemical Water Splitting | |
| Zahran et al. | Solar‑Driven in H PVE 2 Production Systems | |
| WO2014039798A1 (en) | Light-driven hydroiodic acid splitting from semiconductive fuel generator | |
| JP2011116625A (en) | Hydrogen producing apparatus and hydrogen producing method | |
| Shaner | An Experimental and Technoeconomic Study of Silicon Microwire Arrays for Fuel Production Using Solar Energy | |
| JP2011162428A (en) | Apparatus and method for producing hydrogen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |