WO2018076886A1 - 光补电电解水制氢微电极光纤、光缆及制氢装置 - Google Patents

光补电电解水制氢微电极光纤、光缆及制氢装置 Download PDF

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Publication number
WO2018076886A1
WO2018076886A1 PCT/CN2017/096154 CN2017096154W WO2018076886A1 WO 2018076886 A1 WO2018076886 A1 WO 2018076886A1 CN 2017096154 W CN2017096154 W CN 2017096154W WO 2018076886 A1 WO2018076886 A1 WO 2018076886A1
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Prior art keywords
light guiding
microelectrode
light
hydrogen
optical fiber
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Ceased
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PCT/CN2017/096154
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English (en)
French (fr)
Inventor
陈义龙
张岩丰
陶磊明
杜富滢
周欢欢
郑兴才
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Zhongying Changjiang International New Energy Investment Co Ltd
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Zhongying Changjiang International New Energy Investment Co Ltd
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Priority to BR112019008555-6A priority Critical patent/BR112019008555A2/pt
Priority to MYPI2019002349A priority patent/MY190009A/en
Priority to MX2019004817A priority patent/MX2019004817A/es
Priority to KR1020197015240A priority patent/KR20190073502A/ko
Priority to AU2017348218A priority patent/AU2017348218B2/en
Priority to JP2019522490A priority patent/JP6948393B2/ja
Priority to CA3041558A priority patent/CA3041558A1/en
Priority to EP17864147.8A priority patent/EP3533904A4/en
Application filed by Zhongying Changjiang International New Energy Investment Co Ltd filed Critical Zhongying Changjiang International New Energy Investment Co Ltd
Priority to RU2019116002A priority patent/RU2019116002A/ru
Publication of WO2018076886A1 publication Critical patent/WO2018076886A1/zh
Priority to US16/395,280 priority patent/US20190249314A1/en
Anticipated expiration legal-status Critical
Priority to ZA2019/03289A priority patent/ZA201903289B/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • 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
    • 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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the invention relates to a hydrogen production device, in particular to a light-charge electrolysis water-hydrogen microelectrode optical fiber, an optical cable and a hydrogen production device.
  • Hydrogen is used as a secondary energy source and must be prepared by a certain method.
  • the traditional hydrogen production methods mainly include the reforming of fossil fuels, industrial by-product hydrogen production and electrolysis of water to produce hydrogen.
  • Hydrogen production from electrolyzed water is the use of electrical energy to break down water and obtain hydrogen.
  • the purity of hydrogen obtained by the electrolysis water method is high, which can reach 99.98%, but the electricity consumed in this process is very high.
  • 1Nm 3 hydrogen is electrolyzed industrially, and the power consumption is about 4 to 5 degrees, and the efficiency is about 50% to 70%. .
  • electrolytic hydrogen production indirectly produces a large amount of greenhouse gases, CO 2 and other pollutants.
  • Solar hydrogen production is a system that uses solar energy to produce hydrogen. It mainly produces hydrogen by photolysis, and solar power combines with electrolyzed water to produce hydrogen. Compared to traditional technical methods, such systems have great potential to reduce the cost of electrolytic hydrogen.
  • the foundation and application research and development plan for materials science and system engineering of photoelectrochemical cells are being carried out around the world. To date, the exemplary solar-hydrogen conversion efficiency has reached 16%.
  • Chinese Patent Application, Publication No. CN102534645A discloses a photocatalytic method for assisting electrolysis of water to produce hydrogen.
  • the anode of the electrolytic cell is modified by a photocatalytic material, and the anode is irradiated with a light source.
  • a photocatalytic process is coupled to realize photocatalytic auxiliary electrolysis of water to produce hydrogen.
  • the invention organically couples photocatalysis with electrolyzed water to produce a synergistic effect, reducing the cell voltage and hydrogen production power consumption.
  • the invention only proposes the idea of photo-charged hydrogen production, which is less involved in its practical application, and does not provide a hydrogen production device that can be industrially applied.
  • the object of the present invention is to provide a high-efficiency and energy-saving light-charge electrolysis water-hydrogen microelectrode fiber, an optical cable and a hydrogen-making device, which use clean solar energy to supplement part of the energy of electrolysis of water to produce hydrogen.
  • the light-charged electrolysis water-making hydrogen microelectrode optical fiber designed by the invention comprises a light guiding inner core,
  • the light guiding inner core has at least a first light guiding segment extending rearward from a front end thereof and a second light guiding segment behind the first light guiding segment, wherein the first light guiding segment is a circumferential wall surface transparent segment
  • the second light guiding segment is a circumferential wall surface transmissive segment or an opaque segment;
  • the light guiding inner core is provided with a light absorbing layer, an inner electrode layer and an insulating layer on the first light guiding segment thereof from the inside to the outside.
  • the light absorbing layer is a photovoltaic material layer which is excited by light to generate electrons, and can transmit light from the light guiding core
  • the inner electrode layer and the proton exchange membrane are connected to the plurality of microelectrodes of the void layer through the insulating layer, and the plurality of microelectrodes are evenly distributed around the inner electrode layer;
  • the outer electrode layer is porous conductive
  • the light guiding inner core is provided with a conductive layer on the second light guiding section thereof, and the conductive layer is connected to the inner electrode layer.
  • the microelectrode fiber only needs to immerse its first light guiding section into the existing electrolyte tank, and connect or pass the second light guiding section and the outer electrode layer respectively to the positive and negative poles of the external power source.
  • the grounding method is indirectly connected to form a complete electrolytic cell; at the same time, the light guiding inner core introduces light energy, and the light absorbing layer is excited to generate electrons to form a photovoltaic cell, which supplements the consumed electric energy.
  • the conductive layer and the inner electrode layer are integrally formed by the same conductive material.
  • the light guiding core further has a third light guiding segment behind the second light guiding segment, and the third light guiding segment is a circumferential wall opaque segment.
  • the inner guiding layer of the light guiding inner core at the first end of the first light guiding section is sealed by an insulating layer, and the entire end may be covered and sealed by an insulating material. If it is not sealed, a small amount of electric energy may be lost due to leakage, but since the reaction of the internal electrode layer is mainly concentrated on the microelectrode due to the catalysis, and the exposed area is small, the leakage loss is small and can still be implemented.
  • the light absorbing layer has a thickness of 50 nm to 20 ⁇ m
  • the inner electrode layer has a thickness of 50 nm to 50 ⁇ m
  • the insulating layer has a thickness of 10 nm to 50 ⁇ m
  • the microelectrode has a radius of 100 nm to 20 ⁇ m.
  • the proton exchange membrane has a thickness of 0.05 to 0.5 mm.
  • the light guiding inner core is a material having a high-throughput transmission property of light along the surface, such as a quartz fiber, a plastic fiber, a crystal fiber, a polymer material light pipe, a glass light pipe, a glass fiber or a transparent mica fiber.
  • the light guiding inner core has an elongated linear shape, which is solid or hollow, and the cross-sectional area thereof may be a circular shape, a rectangular shape (such as a light guiding tape), or the like.
  • the microelectrode is a Pt electrode, a Pd electrode or an Fe electrode containing NiS.
  • the microelectrode may penetrate the insulating layer by means of photolithography or the like and be connected to the inner electrode layer.
  • the microelectrode corresponds to the extension of the inner electrode layer, increases the reaction area of the internal electrode, and plays a catalytic role.
  • the material when the inner electrode layer or the outer electrode layer is used as a cathode, the material is Pt, Pd, Cu, Al, graphene, Ti, Tl, Cr or Au, and when the anode is used as a cathode, the material is C or a catalyst.
  • the catalyst is one or more of an oxide of iron, an oxide of cobalt, and an oxide of nickel.
  • the microelectrode fiber of the invention is divided into two types according to the position of the anode and the cathode, one is a cathode (ie, an inner electrode layer), the anode is outside (ie, an outer electrode layer); the other is an anode and the cathode is outside;
  • a cathode ie, an inner electrode layer
  • the anode is outside (ie, an outer electrode layer)
  • the other is an anode and the cathode is outside
  • the cathode When connecting an external power supply, the cathode is connected to the negative pole and the anode is connected to the positive pole
  • the light absorbing layer is a divalent cerium salt organic dye using dicarboxybipyridine, and a light absorbing layer formed on the surface of the light guiding core by metal organic vapor deposition or chemical vapor deposition, wherein chemical vapor deposition is optimal,
  • the organic dye and the organic viscose are mixed under vacuum to form a light absorbing layer formed on the surface of the light guiding core.
  • the light absorbing layer is a light absorbing layer formed on the surface of the light guiding core by vacuum spraying, vacuum sputtering, thermal evaporation or physical vapor deposition using an inorganic semiconductor material;
  • the inorganic semiconductor material is TiO 2 , ZnS, CdSe, MoS, CuInS or GaInP; preferably n-type TiO 2 , ZnS or CdSe quantum dots having a particle diameter of 5 to 10 nm, and the three-dimensional scale is on the order of nanometers (0.1 to 100 nm).
  • the material of the insulating layer is silicon dioxide, silicon nitride, polyimide or parylene.
  • the proton exchange membrane is a perfluorosulfonic acid membrane (Nifion membrane), a sulfonated polystyrene membrane, a modified perfluorosulfonic acid polymer membrane or 1-butyl-3-methylimidazolium fluoride One of the methanesulfonic acid membranes.
  • the electrolyte is water, an acidic solution, an alkaline solution or an aqueous solution containing an electrolytic activator, and the acidity and basicity of the electrolyte are tolerated by the proton exchange membrane.
  • the present invention also provides a light-filled electrolysis water hydrogen cable, including a protective sleeve, which is covered with an axis along the shaft.
  • a plurality of microelectrode fibers arranged in a bundle shape adjacent to each other, wherein the microelectrode fibers are the above-mentioned photo-charged electrolysis water-hydrogen microelectrode fibers.
  • a plurality of the microelectrode fibers are arranged in close proximity in the protective sleeve, and the close proximity has the advantage that the entire outer hydrogen fiber optic cable is directly or indirectly connected to the external power source after the entire hydrogen production cable is cut open. It is possible to realize the conduction of all the microelectrode fibers and the external power source, and it is not necessary to separately connect the power source to each of the microelectrode fibers, which is convenient for operation.
  • the present invention also provides a photocharged electrolysis water hydrogen production device, including an electrolyte tank, a hydrogen production cable, an internal electrode bus, an external electrode bus, and a fiber dispersion.
  • the hydrogen-producing cable is the above-mentioned light-charged electrolysis water-hydrogen cable for electrolysis to produce hydrogen into the electrolyte tank;
  • the protective sleeve of the hydrogen-producing cable is in a bundle-shaped micro-correlation a first end of the first light guiding segment of the electrode fiber is cut away to expose an outer electrode layer on the outer surface of the first light guiding segment;
  • the protective sleeve of the hydrogen producing cable is bundled corresponding thereto a second light guiding section of the microelectrode fiber is cut away to expose a conductive layer on the outer surface of the second light guiding section;
  • the first light guiding section of the bundled microelectrode fiber is dispersed by the fiber dispersion device Soaking in the electrolyte of the electrolyte tank, and the outer electrode layer on the outer surface of each first light guiding section is electrically connected to the outer electrode busbar;
  • the second light guiding section of the bundled microelectrode fiber is arranged in
  • the number of the hydrogen-producing cables is plural, and the array is distributed above the electrolyte tank.
  • the optical fiber dispersing device comprises an upper array aperture plate and a lower array aperture plate fixedly disposed in an electrolyte solution tank, wherein the upper array aperture plate and the lower array aperture plate are provided with a plurality of upper and lower corresponding arrays
  • the first optical guiding section of each of the microelectrode fibers is fixed by two corresponding optical fiber fixing holes.
  • the upper array of orifice plates is an insulator;
  • the lower array of orifice plates is an electrical conductor, and serves as an outer electrode confluence member, through the optical fiber fixing holes thereon and the outer surface of the first light guiding section of each microelectrode optical fiber
  • the outer electrode layer is connected;
  • the inner electrode bus is a cable interface copper ring, and the sleeve is placed on the second light guiding section of the bundled microelectrode fiber after cutting the protective sleeve, and is electrically conductive on the outer surface thereof
  • the layers are in contact.
  • the upper portion of the electrolyte tank is further provided with a defoaming net.
  • the invention improves the structural design by introducing new materials, improves and improves the parameters of the indexes, and further obtains an electrolysis water hydrogen production method with economic value.
  • the decomposition voltage Ed of hydrogen produced by electrolysis of water is constant, and is mainly supplied by an electric field.
  • the supplemental energy is provided by the solar energy, thereby reducing the power consumption.
  • H oxygen overpotential of hydrogen and oxygen hydrogen h with the relevant material, a reasonable choice of a low hydrogen overvoltage and low oxygen overpotential material, lower power consumption.
  • Due to low hydrogen and oxygen overpotential materials such as Pt, Pd, Co, Ni, Cu and other metal materials, most of them are precious metals, which are expensive.
  • the size of the microelectrodes is very small and the amount of material used is small, so we can boldly use materials with good performance without too much attention to cost.
  • the ohmic pressure drop IR solution of the solution reduces the solution resistance by using a "zero gap" proton exchange membrane.
  • Electrode ohmic pressure drop IR u the relationship between current and electrode radius
  • microelectrodes, membranes, porous materials and other techniques to reduce the volume V of the design cell; using multiple microelectrode arrays, electrons are transferred along the metal surface, increasing the electrode area A, increasing the space-time yield A/V value, increasing The amount of product obtained per unit time of the electrolysis cell per unit volume.
  • the beneficial effects of the invention are: 1) improving the electrical energy efficiency by using microelectrodes, proton exchange membranes and porous technology, using solar energy as a supplement of electric energy, effectively reducing power consumption and increasing space time yield; 2) microelectrode The fiber diameter is small, the specific surface area of the electrode reaction is large, the material usage can be reduced, the cost can be reduced, and the conventional electrolyzed water is uneconomical; 3) the hydrogen production device can install a plurality of hydrogen production cables in an array on an electrolyte tank.
  • the electrode is made into the form of optical fiber and optical cable, which is easy to mass-produce, easy to use, and can increase or decrease the scale of hydrogen production at any time.
  • FIG. 1 is a schematic view showing the structure of a light-charged electrolysis water hydrogen producing apparatus in Examples 1 to 4.
  • FIG. 2 is a schematic structural view of the hydrogen cable of FIG. 1 taken transversely.
  • FIG. 3 is a schematic structural view of the microelectrode fiber of FIG. 2 taken along a central axis.
  • FIG. 4 is a schematic structural view of the microelectrode fiber of FIG. 3 taken along a transverse direction of the first light guiding section.
  • FIG. 5 is a top plan view of the upper array orifice plate/lower array orifice plate of FIG. 1.
  • Fig. 6 is a schematic plan view showing the structure of a light-charged electrolysis water hydrogen producing apparatus in the fifth embodiment.
  • FIG. 7 is a schematic diagram of the electrolysis principle of the single microelectrode fiber of FIG. 3, which is a schematic diagram, not an actual electrolytic cell.
  • microelectrode fiber 1 first light guiding segment A, second light guiding segment B, third light guiding segment C, light guiding inner core 2, light absorbing layer 3, inner electrode layer 4, insulating layer 5, void layer 6
  • hydrogen producing cable 11 protective sleeve 12
  • electrolyte tank 13 electrolyte 14
  • cable interface copper ring 15 auxiliary positioning net 16
  • upper Array orifice plate 17 lower array orifice plate 18
  • fiber fixing hole 19 defoaming net 20
  • gas outlet 21 water inlet 22, water outlet 23, waste liquid discharge port 24, external power source 25, wire 26
  • the light-charged electrolysis water hydrogen production apparatus includes an electrolyte tank 13, a hydrogen-producing cable 11, an internal electrode confluence member, an external electrode confluence member, and a fiber dispersion device.
  • the various parts are specified as follows:
  • the hydrogen-producing cable 11 includes a protective sleeve 12 which is covered with a plurality of microelectrode fibers 1 arranged in close proximity in the axial direction to be bundled.
  • the microelectrode optical fiber 1 includes a light guiding inner core 2, and the light guiding inner core 2 is sequentially divided into three segments of a first light guiding segment A, a second light guiding segment B and a third light guiding segment C.
  • the light guiding inner core 2 transmits light in the circumferential wall surface of the first light guiding section A, and is opaque to the circumferential wall surface of the second light guiding section B and the third light guiding section C.
  • the light guiding core 2 is provided with a light absorbing layer 3, an inner electrode layer 4, an insulating layer 5, a proton exchange film 8 and an outer electrode layer 9, and an insulating layer 5 and a proton exchange film 8 in this order from the inside to the outside in the first light guiding section A.
  • a void layer 6 is formed between them.
  • the inner electrode layer 4 and the proton exchange membrane 8 are connected to the plurality of microelectrodes 7 of the void layer 6 through the insulating layer 5, and the plurality of microelectrodes 7 are distributed around the array of the inner electrode layers 4.
  • the outer electrode layer 9 is a porous conductive structure.
  • the inner electrode layer of the first end of the first light guiding section A is covered and sealed by the insulating layer 5.
  • the light guiding core 2 is provided with a conductive layer 10 in the second light guiding section B, and the conductive layer 10 is extended from the inner electrode layer 4 to the second light guiding section B.
  • the light absorbing layer 3 is in the second light guiding section.
  • the third light guiding segment C includes only the light guiding inner core 2, and does not include layers such as the light absorbing layer 3.
  • the light guiding core 2 is made of a special quartz fiber having a high-throughput transmission characteristic of light along the surface, and an anti-reflection film is plated on a portion of the third light guiding section C.
  • the outer electrode layer 9 serves as an anode, and the material thereof is selected to be a porous carbon layer on which an iron oxyhydroxide catalyst is mounted.
  • the inner electrode layer 4 serves as a cathode, and vacuum-sputtering a layer of conductive Cu having a thickness of 500 nm for transmitting a power source current and collecting an electron current generated by the light absorbing layer 3.
  • the material of the light absorbing layer 3 was selected to be n-type TiO 2 , and the light absorbing layer 3 was formed on the light guiding core 2 by vacuum spraying to a thickness of 500 nm.
  • the material of the insulating layer 5 was selected to be silicon dioxide and had a thickness of 1 ⁇ m.
  • the material of the microelectrode 7 is selected to be Pt and the radius is 100 nm.
  • the microelectrodes 7 distributed in the array are prepared in the insulating layer 5 by photolithography.
  • the proton exchange membrane 8 was selected as a Nifion membrane which functions to allow proton conduction, isolating oxygen and hydrogen, and has a thickness of 0.1 mm.
  • the hydrogen-producing cable 11 penetrates and is fixed from the top of the electrolytic solution tank 13, and includes one end of the first light guiding section A which projects into the electrolytic solution 14 in the electrolytic solution tank 13.
  • the protective sleeve 12 of the hydrogen-producing cable 11 is partially cut away from the first light guiding section A and the second light guiding section B of the microelectrode optical fiber 1 to expose the microelectrode optical fiber 1 therein.
  • each microelectrode fiber 1 is dispersed and immersed in the electrolyte 14 by a fiber dispersion device, and the outer electrode layer 9 of each microelectrode fiber 1 is electrically connected to the outer electrode bus.
  • the conductive layer 10 of each microelectrode fiber 1 is electrically connected to the internal electrode bus.
  • the fiber dispersion device includes an upper array orifice plate 17 and a lower array orifice plate fixedly disposed above and below the electrolyte tank 13 18, the upper array aperture plate 17 and the lower array aperture plate 18 are provided with a plurality of optical fiber fixing holes 19 correspondingly arranged in an array, and the first light guiding segments of each microelectrode optical fiber 1 are fixed through the upper and lower corresponding two optical fibers.
  • the hole 19 is fixed thereto.
  • the upper array orifice plate 17 is an insulator.
  • the lower array orifice plate 18 is an electrical conductor and serves as an outer electrode busbar, and is connected to the outer electrode layer 9 of each microelectrode fiber 1 on the outer surface of the first light guiding section A through the optical fiber fixing hole 19 thereon, and further passes through
  • the wire 26 is connected to an external power source 25.
  • the inner electrode busbar is a cable interface copper ring 15, which is sleeved on the second light guiding section B of the bundled microelectrode fiber 1 after the protective sleeve 12 is cut away, and is in contact with the conductive layer 10 on the outer surface thereof.
  • the cable interface copper ring 15 is further connected to the external power source 25 via a wire 26.
  • the fiber dispersion device is composed of an upper array orifice plate 17, a lower array orifice plate 18, and a fiber fixing hole 19.
  • An auxiliary positioning net 16 is disposed between the upper array aperture plate 17 and the lower array aperture plate 18.
  • the microelectrode optical fiber 1 passes through the mesh, and the effect is equivalent to the multilayer array aperture plate, and the microelectrode optical fiber 1 can be reinforced. The stability of the part between the two orifice plates.
  • the electrolyte tank 13 is further provided with a gas outlet 21, a water inlet 22, a water outlet 23, a waste liquid discharge port 24, and a defoaming net 20.
  • the H 2 , O 2 , etc. produced by the electrolysis are output through the gas outlet 21 and further sent to the gas separation system for separation.
  • the light-guiding inner core 2 is a flat light guide strip, and the material of the light-absorbing layer 3 is selected as a 5 nm CdSe quantum dot, and the other is the same as in the first embodiment.
  • the material of the internal electrode layer 4 is graphene, and the other is the same as that of the first embodiment.
  • the material 8 of the microelectrode 8 is an Fe electrode containing NiS, and other parameters are the same as in the first embodiment.
  • the light-charged electrolysis water hydrogen production device provided in this embodiment has six hydrogen-producing cables 11 and an array distribution (3 ⁇ 2) on the electrolyte tank 13, and other embodiments. 1 is the same.
  • the isolated single light guiding inner core 2 is the research object, and the electrolytic cell formed thereof is as shown in FIG.
  • the working process is as follows:
  • the light guiding core 2 absorbs light energy in the third light guiding section C, and transmits the light energy to the light absorbing layer 3 of the first light guiding section A.
  • the light absorbing layer 3 absorbs light energy and generates electrons, and electrons are transmitted to the cathode ( Inner electrode layer 4).
  • the negative electrode of the external power source 25 also delivers electrons to the cathode.

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Abstract

一种光补电电解水制氢微电极光纤(1)、光缆(11)及制氢装置，该微电极光纤(1)包括导光内芯(2)，导光内芯(2)至少具有第一导光段(A)和第二导光段(B)；导光内芯(2)在第一导光段(A)由内而外依次设置有吸光层(3)、内电极层(4)、绝缘层(5)、空隙层(6)、质子交换膜(8)和外电极层(9)；导光内芯(2)在第二导光段(B)设置有与内电极层(4)相连的导电层(10)。该制氢光缆(11)包括保护套管(12)和包覆在其内呈集束状的微电极光纤(1)。该制氢装置包括电解液槽(13)、制氢光缆(11)、内电极汇流件、外电极汇流件和光纤分散装置；制氢光缆(11)的各微电极光纤(1)分散到电解液(14)内；各微电极光纤(1)的外电极层(9)、导电层(10)分别与内电极汇流件、外电极汇流件电连接。该制氢装置利用太阳能作为电能的补充，有效降低了电能消耗，增加了氢气的空时产率。

Description

光补电电解水制氢微电极光纤、光缆及制氢装置 技术领域
本发明涉及一种制氢装置，特别是指一种光补电电解水制氢微电极光纤、光缆及制氢装置。
背景技术
氢气作为二次能源，必须通过一定方法才能将它制备出来。制氢方法很多，传统的制氢方法主要有化石燃料的重整、工业副产氢气和电解水制氢。
电解水制氢就是利用电能来分解水，获得氢气。通过电解水方法得到氢气纯度较高，可达到99.98％，但是这个过程耗费的电量很高，目前工业上电解1Nm3氢气，约耗电量4～5度电，效率约为50％～70％。考虑到目前的供电以煤电为主，电解制氢间接产生了大量温室气体CO2和其他污染物。
太阳能制氢是利用太阳能生产氢气的系统，主要有光分解制氢，太阳能发电结合电解水制氢两类。和传统的技术方法相比，这类系统有很大的潜力可以减少电解氢成本。目前全球正在开展光电化学池材料科学和系统工程的基础和应用研发计划。迄今示范型太阳能-氢气转换效率可达16％。
中国专利申请，公布号CN102534645A，公开了一种光催化辅助电解水制氢的方法，以工业化的电解水制氢装置为基础，通过光催化材料对电解池阳极进行修饰，并采用光源辐照阳极，在电解水的过程中耦合光催化过程，实现光催化辅助电解水制氢。该发明将光催化与电解水有机地耦合在一起，产生协同效应，降低了电解池电压和制氢电耗。然而，该发明仅仅提出了光补电制氢的思路，对其实际应用涉及较少，并且没有提供可工业化应用的制氢装置。
发明内容
本发明的目的在于提供一种高效、节能的光补电电解水制氢微电极光纤、光缆及制氢装置，利用清洁太阳能补充电解水制氢的部分能量。
为实现上述目的，本发明所设计的光补电电解水制氢微电极光纤，包括导光内芯， 所述导光内芯至少具有由其首端向后延伸的第一导光段和位于第一导光段后面的第二导光段，所述第一导光段为周向壁面透光段，所述第二导光段为周向壁面透光段或不透光段；所述导光内芯在其第一导光段上由内而外依次设置有吸光层、内电极层、绝缘层、质子交换膜和外电极层，所述绝缘层与质子交换膜之间形成有空隙层；所述吸光层为受光能激发产生电子的光伏材料层，可将导光内芯传来的光能转换成电能；所述内电极层与质子交换膜通过穿透绝缘层与空隙层的多个微电极相连，所述多个微电极环绕内电极层均匀分布；所述外电极层为多孔导电结构；所述导光内芯在其第二导光段上设置有导电层，所述导电层与内电极层相连。
该微电极光纤在具体应用时，只需将其第一导光段浸入到现有的电解液槽中，并将第二导光段、外电极层分别与外部电源的正负极相连或通过接地的方式间接相连，形成完整的电解池；同时导光内芯将光能导入，激发吸光层产生电子形成光电池，补充消耗的电能。
优选地，所述导电层与内电极层由相同的导电材料一体化制作成型。
所述导光内芯还具有位于第二导光段后面的第三导光段，所述第三导光段为周向壁面不透光段。
优选地，所述导光内芯在其第一导光段首端的内电极层通过绝缘层包覆密封，也可以采用绝缘材料将整个端部包覆密封。若不密封可能因为漏电损失少量电能，但由于催化作用内电极层的反应主要集中在微电极上，且露出的面积很小，因此漏电损失较小，仍然能够实施。
优选地，所述吸光层的厚度为50nm～20μm，所述内电极层的厚度为50nm～50μm，所述绝缘层的厚度为10nm～50μm，所述微电极的半径为100nm～20μm，所述质子交换膜的厚度为0.05～0.5mm。
优选地，所述导光内芯为石英光纤、塑料光纤、晶体光纤、高分子材料光导管、玻璃光导管、玻璃光纤或透光云母光纤等具有光沿表面高通量传输特性的物质。导光内芯为细长的线形，实心、空心皆可，其横截面积可以是圆形、长方形(如光导带)等。
优选地，所述微电极为Pt电极、Pd电极或含有NiS的Fe电极。微电极可以采用光刻蚀压印技术等方式穿透绝缘层并连接到内电极层上，微电极相当于内电极层的延伸，增大了内部电极的反应面积，并且起到催化作用。
优选地，所述内电极层或外电极层作为阴极时其制作材料为Pt、Pd、Cu、Al、石墨烯、Ti、Tl、Cr或Au，作为阳极时其制作材料为搭载催化剂的C或Ni，所述催化剂为铁的氧化物、钴的氧化物、镍的氧化物中的一种或多种。本发明微电极光纤根据阴阳极的位置不同分为两种类型，一种是阴极在内(即内电极层)、阳极在外(即外电极层)；另一种是阳极在内、阴极在外；连接外部电源时阴极连接负极，阳极连接正极。
优选地，所述吸光层是采用二羧基联吡啶的二价钌盐有机染料，通过金属有机气相沉积或化学气相沉积，在导光内芯表面形成的吸光层，其中以化学气相沉积最优，或者是在真空条件下将所述有机染料与有机粘胶混合甩膜在导光内芯表面形成的吸光层。
优选地，所述吸光层是采用无机半导体材料，通过真空喷涂、真空溅射、热蒸镀或物理气相沉积在导光内芯表面形成的吸光层；所述无机半导体材料为TiO2、ZnS、CdSe、MoS、CuInS或GaInP；优选为n型TiO2，ZnS或粒径为5～10nm的CdSe量子点，三维尺度都在纳米级(0.1～100nm)。
优选地，所述绝缘层的材料为二氧化硅、氮化硅、聚酰亚胺或聚对二甲苯。
优选地，所述质子交换膜为全氟磺酸隔膜(Nifion膜)、磺酸基化聚苯乙烯膜、改性全氟磺酸聚合物膜或1-丁基-3-甲基咪唑三氟甲基磺酸膜中的一种。
可选地，所述电解液为水、酸性溶液、碱性溶液或含电解活化剂的水溶液，电解液的酸、碱性质要以质子交换膜可承受为准。
考虑到单根微电极光纤很细，为便于使用和保护微电极光纤，本发明同时提供了一种光补电电解水制氢光缆，包括保护套管，所述保护套管内包覆有沿轴向相邻布置而呈集束状的多根微电极光纤，所述微电极光纤为前述光补电电解水制氢微电极光纤。优选地，在保护套管内多根所述微电极光纤紧密相邻布置，紧密相邻的好处是使整个制氢光缆剖开外层后只要最外侧的微电极光纤直接或间接的与外接电源相连，就能实现全部微电极光纤与外接电源导通，不必对每根微电极光纤分别连接电源，方便操作。
基于前述微电极光纤和制氢光缆的具体应用，本发明还提供了一种光补电电解水制氢装置，包括电解液槽、制氢光缆、内电极汇流件、外电极汇流件和光纤分散装置；所述制氢光缆为前述光补电电解水制氢光缆，用于伸入到电解液槽中电解制氢；所述制氢光缆的保护套管在对应于其内呈集束状的微电极光纤的第一导光段首端剖开一段，从而暴露出第一导光段外表面上的外电极层；所述制氢光缆的保护套管在对应于其内呈集束 状的微电极光纤的第二导光段剖开一段，从而暴露出第二导光段外表面上的导电层；所述呈集束状的微电极光纤的第一导光段通过光纤分散装置分散浸泡在电解液槽的电解液中，且各第一导光段外表面上的外电极层与外电极汇流件电连接；所述呈集束状的微电极光纤的第二导光段布置在电解液槽的外面，且各第二导光段外表面上的导电层与内电极汇流件电连接。
优选地，所述制氢光缆的数量为多根，阵列分布在电解液槽的上方。
优选地，所述光纤分散装置包括上下固定设置在电解液槽内的上阵列孔板和下阵列孔板，所述上阵列孔板和下阵列孔板上开设有上下对应且阵列分布的多个光纤固定孔，每根所述微电极光纤的第一导光段通过上下对应的两个光纤固定孔进行固定。
优选地，所述上阵列孔板为绝缘体；所述下阵列孔板为导电体，并作为外电极汇流件，通过其上的光纤固定孔与各微电极光纤的第一导光段外表面上的外电极层相连；所述内电极汇流件为电缆接口铜环，箍套在剖去保护套管后的呈集束状的微电极光纤的第二导光段上，并与其外表面上的导电层相接触。
优选地，所述电解液槽的上部还设置有除泡网。
本发明设计原理：
一个电化学过程是否有实用价值的经济效益，常用转化率、电流效率、电能消耗和空时产率等指标来评价。本发明通过引入新材料，优化结构设计，改进完善这几个指标参数，进而获得具有可实现经济价值的电解水制氢方法。
为阐释本发明电解水制氢怎样提高经济价值，首先列出电解水原理：
1)反应原理
在酸性溶液电解时，
阴极：
Figure PCTCN2017096154-appb-000001
阳极：
Figure PCTCN2017096154-appb-000002
在碱性溶液中电解时，
阴极：
Figure PCTCN2017096154-appb-000003
阳极：
Figure PCTCN2017096154-appb-000004
两种情况下的总反应均为：
Figure PCTCN2017096154-appb-000005
2)槽电压
Figure PCTCN2017096154-appb-000006
槽电压(合计)V＝Ed+h氧+h氢+∑IR
由上述知，当电流效率一定时，电压的大小决定了电能消耗多少。
在反应条件一定的情况下，电解水制氢的分解电压Ed为定值，主要由电场提供。通过利用光催化材料给予电解电极一定电压补偿，补充的能量由太阳能提供，从而降低电能消耗。
氢和氧的过电位h氧、h氢跟材料有关，选择合理的低氢过电位和低氧过电位材料，降低电能消耗。由于低氢和氧过电位材料如Pt、Pd、Co、Ni、Cu等金属材料，大多为贵金属，价格昂贵。微电极的尺寸非常小，对材料使用量很少，由此我们可大胆使用性能好的材料，而不过多顾虑成本问题。
溶液的欧姆压降IR溶液，通过使用“零间隙”的质子交换膜，从而降低溶液电阻。
气泡的效应压降IR气体，通过利用多孔材料，降低气泡表面涨力，减少气泡产生量，从而降低气泡的效应压降。
电极欧姆压降IRu，从电流与电极半径关系公式
Figure PCTCN2017096154-appb-000007
可以看出，当电流达到稳态时，电极半径越小，电流越小，可以忽略电极欧姆压降，则无需再进行电压调试，可以省去参比电极，节约电解槽设计空间。
微电极、膜、多孔材料等技术的使用，降低设计电解槽体积V；使用多根微电极阵列布置，电子沿金属表面传递，增大电极面积A，提高空时产率A/V值，增加单位体积的电解槽在单位时间内所得产物的量。
本发明的有益效果是：1)通过使用微电极、质子交换膜和多孔技术，来提高电能效率，利用太阳能作为电能的补充，有效降低了电能消耗，增加了空时产率；2)微电极光纤直径小，电极反应的比表面积大，能够减少材料使用量，降低成本，解决传统电解水不经济问题；3)该制氢装置可在一个电解液槽上阵列的安装多个制氢电缆，也可作为集成模块的使用，实现电解水制氢的大规模应用；4)可以在相当高的电流密度下操作，而槽电压很低，电解1Nm3氢气，消耗电能在1度左右，电能效率达到90％，空时产率A/V可到200cm-1。5)电极做成光纤和光缆的形式，易于批量化生产，使用方便，并可随时增减制氢规模。
附图说明
图1为实施例1～4中光补电电解水制氢装置的结构示意图。
图2为图1中制氢光缆横向剖开的结构示意图。
图3为图2中微电极光纤沿中轴线剖开的结构示意图。
图4为图3中微电极光纤在第一导光段横向剖开的结构示意图。
图5为图1中上阵列孔板/下阵列孔板的俯视结构示意图。
图6为实施例5中光补电电解水制氢装置的俯视结构示意图。
图7为图3中单根微电极光纤的电解原理示意图，该图为原理图，不是实际存在的电解池。
其中：微电极光纤1、第一导光段A、第二导光段B、第三导光段C、导光内芯2、吸光层3、内电极层4、绝缘层5、空隙层6、微电极7、质子交换膜8、外电极层9、导电层10、制氢光缆11、保护套管12、电解液槽13、电解液14、电缆接口铜环15、辅助定位网16、上阵列孔板17、下阵列孔板18、光纤固定孔19、除泡网20、气体出口21、水入口22、水出口23、废液排口24、外部电源25、导线26
具体实施方式
下面结合附图和具体实施例对本发明作进一步的详细说明。
实施例1
如图1～5所示，本实施例提供的光补电电解水制氢装置，包括电解液槽13、制氢光缆11、内电极汇流件、外电极汇流件和光纤分散装置。各部分具体说明如下：
制氢光缆11包括保护套管12，保护套管12内包覆有沿轴向紧密相邻布置而呈集束状的多根微电极光纤1。
微电极光纤1包括导光内芯2，导光内芯2依次分为第一导光段A、第二导光段B和第三导光段C三段。导光内芯2在第一导光段A周向壁面透光，在第二导光段B、第三导光段C周向壁面不透光。导光内芯2在第一导光段A由内而外依次设置有吸光层3、内电极层4、绝缘层5、质子交换膜8和外电极层9，绝缘层5与质子交换膜8之间形成有空隙层6。内电极层4与质子交换膜8通过穿透绝缘层5与空隙层6的多个微电极7相连，多个微电极7环绕内电极层4阵列分布。外电极层9为多孔导电结构。第一导光段A首端的内电极层通过绝缘层5包覆密封。导光内芯2在第二导光段B设置有导电层10，导电层10由内电极层4向第二导光段B延伸得到，为便于生产制造，吸光层3在第二导光段B也进行了保留，整体上相当于第二导光段B只制作了内电极层4及以内的部分，或者相当于对应于第一导光段A的绝缘层5及以外的部分被剖去了。第三导光段C仅包含导光内芯2，不含吸光层3等各层。
导光内芯2采用具有光沿表面高通量传输特性的特种石英光纤，其在第三导光段C的部分镀有增透膜。外电极层9作为阳极，其材料选择为搭载羟基氧化铁催化剂的多孔碳层。内电极层4作为阴极，采用真空溅射一层厚度为500nm导电Cu，用于传输电源电流和收集吸光层3产生的电子电流。吸光层3的材料选择为n型TiO2，采用真空喷涂在导光内芯2上形成吸光层3，厚度在500nm。绝缘层5的材料选择为二氧化硅，厚度为1μm。微电极7的材料选择为Pt，半径为100nm，采用光刻蚀压印技术，在绝缘层5制备阵列分布的微电极7。质子交换膜8选择为Nifion膜，其作用为容许质子传导，隔离氧气和氢气，其厚度为0.1mm。
制氢光缆11从电解液槽13的顶部穿入并固定，其包含第一导光段A的一端伸入到电解液槽13内的电解液14中。制氢光缆11的保护套管12在微电极光纤1的第一导光段A、第二导光段B剖开一部分并露出其中的微电极光纤1。在第一导光段A，各微电极光纤1通过光纤分散装置分散并浸泡到电解液14内，各微电极光纤1的外电极层9与外电极汇流件电连接。在第二导光段B，各微电极光纤1的导电层10与内电极汇流件电连接。
光纤分散装置包括上下固定设置在电解液槽13内的上阵列孔板17和下阵列孔板 18，上阵列孔板17和下阵列孔板18上开设有上下对应且阵列分布的多个光纤固定孔19，每根微电极光纤1的第一导光段穿过上下对应的两个光纤固定孔19并固定在其上。
上阵列孔板17为绝缘体。下阵列孔板18为导电体，并作为外电极汇流件，通过其上的光纤固定孔19与第一导光段A外表面上的各微电极光纤1的外电极层9相连，并进一步通过导线26与外部电源25相连。内电极汇流件为电缆接口铜环15，箍套在剖去保护套管12后的呈集束状的微电极光纤1的第二导光段B上，并与其外表面上的导电层10相接触，电缆接口铜环15进一步通过导线26与外部电源25相连。
光纤分散装置由上阵列孔板17、下阵列孔板18和光纤固定孔19构成。在上阵列孔板17、下阵列孔板18之间还布置有辅助定位网16，微电极光纤1从其网孔中穿过，效果相当于多层阵列孔板，可加强微电极光纤1位于两孔板之间部分的稳定性。
电解液槽13上还设置有气体出口21、水入口22、水出口23、废液排口24和除泡网20。电解产生的H2、O2等通过气体出口21输出并进一步送到气体分离系统进行分离。
对上述装置进行工作特性测试，分别在未加太阳光照电解水制氢N和加太阳光照电解水制氢Y的条件下进行比较试验，试验光照条件为太阳光，光照强度8万lx，结果如下表：
表1微电极电解制氢工作特性
Figure PCTCN2017096154-appb-000008
由表1可知，在光照补充电子的条件下，可在低电压环境进行较好的制备氢气过程，效率更高，生产的氢气纯度好。
实施例2
本实施例所提供的光补电电解水制氢装置，其导光内芯2采用扁平的光导带，吸光层3的材料选择为5nmCdSe量子点，其他与实施例1相同。
对上述装置进行工作特性测试，分别在未加太阳光照电解水制氢N和加太阳光照电解水制氢Y的条件下进行比较试验，试验光照条件为太阳光，光照强度8万lx，结果如下表：
表2微电极电解制氢工作特性
Figure PCTCN2017096154-appb-000009
由表2可知，在光照补充电子的条件下，可在低电压环境进行较好的制备氢气过程，效率更高，生产的氢气纯度好。
实施例3
本实施例所提供的光补电电解水制氢装置，其内电极层4的材料为石墨烯，其他与实施例1相同。
对该装置进行工作特性测试，分别在未加太阳光照电解水制氢N和加太阳光照电解水制氢Y的条件下进行比较试验，试验光照条件为太阳光，光照强度8万lx，结果如下表：
表3微电极电解制氢工作特性
Figure PCTCN2017096154-appb-000010
由表3可知，在光照补充电子的条件下，可在低电压环境进行较好的制备氢气过程，效率更高，生产的氢气纯度好。
实施例4
本实施例所提供的光补电电解水制氢装置，其微电极8的材料8为含有NiS的Fe电极，其他参数与实施例1相同。
对该装置进行工作特性测试，分别在未加太阳光照电解水制氢N和加太阳光照电解水制氢Y的条件下进行比较试验，试验光照条件为太阳光，光照强度8万lx，结果如下表：
表4微电极电解制氢工作特性
Figure PCTCN2017096154-appb-000011
由表4可知，在光照补充电子的条件下，可在低电压环境进行较好的制备氢气过程，效率更高，生产的氢气纯度好。
实施例5
如图6所示，本实施例所提供的光补电电解水制氢装置，其制氢光缆11的数量为6根，阵列分布(3×2)在电解液槽13上，其他与实施例1相同。
工作原理：
为便于说明上述实施例的工作过程，孤立单根导光内芯2为研究对象，其形成的电解池如图7所示。其工作过程如下：
1)导光内芯2在第三导光段C吸收光能，并将光能传输至第一导光段A的吸光层3，吸光层3吸收光能并产生电子，电子传递至阴极(内电极层4)。外部电源25的负极也将电子传递至阴极。
2)电解液14中的水在阳极(外电极层9)上失去电子，产生氧气和质子，质子通过质子交换膜8传递给微电极7，质子在微电极7上与电子结合生成氢气。氧气从多孔阳极上逸出，氢气从空隙层6逸出。阳极上失去的电子传递给了外部电源25的正极。
3)电解液槽13收集的氢气、氧气等混合气体进一步通过气体分离装置进行分离。

Claims (20)

  1. 一种光补电电解水制氢微电极光纤，其特征在于：包括导光内芯(2)，所述导光内芯(2)至少具有由其首端向后延伸的第一导光段(A)和位于第一导光段(A)后面的第二导光段(B)，所述第一导光段(A)为周向壁面透光段，所述第二导光段(B)为周向壁面透光段或不透光段；
    所述导光内芯(2)在其第一导光段(A)上由内而外依次设置有吸光层(3)、内电极层(4)、绝缘层(5)、质子交换膜(8)和外电极层(9)，所述绝缘层(5)与质子交换膜(8)之间形成有空隙层(6)；所述吸光层(3)为受光能激发产生电子的光伏材料层，可将导光内芯(2)传来的光能转换成电能；所述内电极层(4)与质子交换膜(8)通过穿透绝缘层(5)与空隙层(6)的多个微电极(7)相连，所述多个微电极(7)环绕内电极层(4)均匀分布；所述外电极层(9)为多孔导电结构；
    所述导光内芯(2)在其第二导光段(B)上设置有导电层(10)，所述导电层(10)与内电极层(4)相连。
  2. 根据权利要求1所述的光补电电解水制氢微电极光纤，其特征在于：所述导电层(10)与内电极层(4)由相同的导电材料一体化制作成型。
  3. 根据权利要求1所述的光补电电解水制氢微电极光纤，其特征在于：所述导光内芯(2)还具有位于第二导光段(B)后面的第三导光段(C)，所述第三导光段(C)为周向壁面不透光段。
  4. 根据权利要求1所述的光补电电解水制氢微电极光纤，其特征在于：所述导光内芯(2)在其第一导光段(A)首端的内电极层(4)通过绝缘层(5)包覆密封。
  5. 根据权利要求1所述的光补电电解水制氢微电极光纤，其特征在于：所述吸光层(3)的厚度为50nm～20μm，所述内电极层(4)的厚度为50nm～50μm，所述绝缘层(5)的厚度为10nm～50μm，所述微电极(7)的半径为100nm～20μm，所述质子交换膜(8)的厚度为0.05～0.5mm。
  6. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述导光内芯(2)为石英光纤、塑料光纤、晶体光纤、高分子材料光导管、玻璃光导管、玻璃光纤或透光云母光纤中的一种。
  7. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述微电极(7)为Pt电极、Pd电极或含有NiS的Fe电极。
  8. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述微电极(7)采用光刻蚀压印穿透绝缘层(5)并连接到内电极层(4)上。
  9. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述内电极层(4)或外电极层(9)作为阴极时其制作材料为Pt、Pd、Cu、Al、石墨烯、Ti、Tl、Cr或Au，作为阳极时其制作材料为搭载催化剂的C或Ni，所述催化剂为铁的氧化物、钴的氧化物、镍的氧化物中的一种或多种。
  10. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述吸光层(3)是采用二羧基联吡啶的二价钌盐有机染料，通过金属有机气相沉积或化学气相沉积，在导光内芯(2)表面形成的吸光层(3)；或者是在真空条件下将所述有机染料与有机粘胶混合甩膜在导光内芯(2)表面形成的吸光层(3)。
  11. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述吸光层(3)是采用无机半导体材料，通过真空喷涂、真空溅射、热蒸镀或物理气相沉积，在导光内芯(2)表面形成的吸光层(3)；所述无机半导体材料为TiO2、ZnS、CdSe、MoS、CuInS或GaInP。
  12. 根据权利要求11所述的光补电电解水制氢微电极光纤，其特征在于：所述无机半导体材料为n型TiO2、ZnS或粒径为5～10nm的CdSe量子点。
  13. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述绝缘层(5)的材料为二氧化硅、氮化硅、聚酰亚胺或聚对二甲苯。
  14. 根据权利要求1～5中任一项所述的光补电电解水制氢微电极光纤，其特征在于：所述质子交换膜(8)为全氟磺酸隔膜、磺酸基化聚苯乙烯膜、改性全氟磺酸聚合物膜或1-丁基-3-甲基咪唑三氟甲基磺酸膜。
  15. 一种光补电电解水制氢光缆，包括保护套管(12)，其特征在于：所述保护套管(12)内包覆有沿轴向相邻布置而呈集束状的多根微电极光纤(1)，所述微电极光纤(1)为权利要求1～5中任一项所述的光补电电解水制氢微电极光纤。
  16. 一种光补电电解水制氢装置，包括电解液槽(13)，其特征在于：还包括制氢光缆(11)、内电极汇流件、外电极汇流件和光纤分散装置；所述制氢光缆(11)为权 利要求15所述的光补电电解水制氢光缆，用于伸入到电解液槽(13)中电解制氢；
    所述制氢光缆(11)的保护套管(12)在对应于其内呈集束状的微电极光纤(1)的第一导光段(A)首端剖开一段，从而暴露出第一导光段(A)外表面上的外电极层(9)；所述制氢光缆(11)的保护套管(12)在对应于其内呈集束状的微电极光纤(1)的第二导光段(B)剖开一段，从而暴露出第二导光段(B)外表面上的导电层(10)；
    所述呈集束状的微电极光纤(1)的第一导光段(A)通过光纤分散装置分散浸泡在电解液槽(13)的电解液(14)中，且各第一导光段(A)外表面上的外电极层(9)与外电极汇流件电连接；
    所述呈集束状的微电极光纤(1)的第二导光段(B)布置在电解液槽(13)的外面，且各第二导光段(B)外表面上的导电层(10)与内电极汇流件电连接。
  17. 根据权利要求16所述的光补电电解水制氢装置，其特征在于：所述制氢光缆(11)的数量为多根，阵列分布在电解液槽(13)的上方。
  18. 根据权利要求16所述的光补电电解水制氢装置，其特征在于：所述光纤分散装置包括上下固定设置在电解液槽(13)内的上阵列孔板(17)和下阵列孔板(18)，所述上阵列孔板(17)和下阵列孔板(18)上开设有上下对应且阵列分布的多个光纤固定孔(19)，每根所述微电极光纤(1)的第一导光段(A)通过上下对应的两个光纤固定孔(19)进行固定。
  19. 根据权利要求18所述的光补电电解水制氢装置，其特征在于：所述上阵列孔板(17)为绝缘体；所述下阵列孔板(18)为导电体，并作为外电极汇流件，通过其上的光纤固定孔(19)与各微电极光纤(1)的第一导光段(A)外表面上的外电极层(9)相连；所述内电极汇流件为电缆接口铜环(15)，箍套在剖去保护套管(12)后的呈集束状的微电极光纤(1)的第二导光段(B)上，并与其外表面上的导电层(10)相接触。
  20. 根据权利要求16所述的光补电电解水制氢装置，其特征在于：所述电解液槽(13)的上部还设置有除泡网(20)。
PCT/CN2017/096154 2016-10-26 2017-08-07 光补电电解水制氢微电极光纤、光缆及制氢装置 Ceased WO2018076886A1 (zh)

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MYPI2019002349A MY190009A (en) 2016-10-26 2017-08-07 Hydrogen production microelectrode optical fiber, optical cable, and hydrogen production device for light supplementary electrolysis of water
EP17864147.8A EP3533904A4 (en) 2016-10-26 2017-08-07 HYDROGEN PRODUCTION MICROELECTRODE OPTIC FIBER, OPTICAL CABLE AND HYDROGEN PRODUCTION DEVICE FOR ADDITIONAL ELECTROLYSIS TO WATER LIGHT
RU2019116002A RU2019116002A (ru) 2016-10-26 2017-08-07 Оптоволоконный микроэлектрод для получения водорода, оптический кабель и устройство для получения водорода с поддержкой электролиза воды световой энергией
US16/395,280 US20190249314A1 (en) 2016-10-26 2019-04-26 Optical fiber, optical cable, and hydrogen production device comprising optical cable
ZA2019/03289A ZA201903289B (en) 2016-10-26 2019-05-24 Hydrogen production microelectrode optical fiber, optical cable, and hydrogen production device for light supplementary electrolysis of water

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US11604323B2 (en) 2020-05-21 2023-03-14 Saudi Arabian Oil Company Methods to harvest electromagnetic energy during subsurface high power laser transmission
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AU2017348218B2 (en) 2020-10-22
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EP3533904A1 (en) 2019-09-04
RU2019116002A3 (zh) 2020-11-27
KR20190073502A (ko) 2019-06-26
US20190249314A1 (en) 2019-08-15
CN106435636A (zh) 2017-02-22
AU2017348218A1 (en) 2019-06-13
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BR112019008555A2 (pt) 2019-07-09
RU2019116002A (ru) 2020-11-27
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