CN113337844B - Electrolytic water film electrode, preparation method thereof and hydrogen production device - Google Patents

Electrolytic water film electrode, preparation method thereof and hydrogen production device Download PDF

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CN113337844B
CN113337844B CN202110611066.4A CN202110611066A CN113337844B CN 113337844 B CN113337844 B CN 113337844B CN 202110611066 A CN202110611066 A CN 202110611066A CN 113337844 B CN113337844 B CN 113337844B
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catalyst layer
proton exchange
exchange membrane
catalyst
dehydrogenation
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余丽红
潘牧
田明星
段奔
吴天涯
郑伟倩
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Wuhan Polytechnic Hydrogen Electricity Technology Co ltd
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
    • 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
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    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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    • 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

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Abstract

The application relates to an electrolytic water film electrode, a preparation method thereof and a hydrogen production device, and belongs to the technical field of hydrogen production by water electrolysis. The electrolytic water film electrode comprises a cathode catalyst layer, a proton exchange membrane, a dehydrogenation catalyst layer and an anode catalyst layer which are sequentially stacked. Wherein, the catalyst in the dehydrogenation catalyst layer is a substance containing at least one element of Pt and Pd elements. The electrolytic water film electrode can fulfill the aim of hydrogen elimination on the anode side so as to improve the purity of oxygen on the anode side; at the same time, the amount of oxygen diffusing to the cathode side of the anode side can be reduced (even eliminated), and the purity of the hydrogen on the cathode side is improved.

Description

Electrolytic water film electrode, preparation method thereof and hydrogen production device
Technical Field
The application relates to the technical field of hydrogen production by water electrolysis, in particular to an electrolytic water film electrode, a preparation method thereof and a hydrogen production device.
Background
The electrolytic water membrane electrode is an important component of a PEM (polymer electrolyte membrane) water electrolysis device and comprises a proton exchange membrane, an anode catalyst layer on the anode side of the proton exchange membrane and a cathode catalyst layer on the cathode side of the proton exchange membrane. The working principle of the electrolytic water film electrode is as follows:
cathode: 2H++2e-→H2 (1)
Anode: h2O→1/2O2+2H++2e- (2)
And (3) total reaction: h2O→H2+1/2O2 (3)
Therefore, the anode side of the proton exchange membrane is provided with oxygen gas, the cathode side is provided with hydrogen gas, and the proton exchange membrane in the current electrolytic water membrane electrode basically adopts Nafion117, nafion115 or Nafion212 membranes, and the thickness of the Nafion membranes is 178 μm, 127 μm or 51 μm respectively. Although the thinner the membrane, the lower the voltage loss of the internal resistance of the membrane, thereby lowering the cell voltage and improving the electrolysis efficiency, the thinner Nafion membrane increases the gas permeability, and the hydrogen gas produced at the cathode penetrates through the membrane to the anode side under a high-pressure working environment, resulting in a small amount of hydrogen gas mixed in the oxygen gas, which causes a safety problem when a certain concentration is accumulated.
The traditional dehydrogenation method comprises two methods: one is external dehydrogenation, a set of dehydrogenation device is added at an oxygen outlet of an electrolytic cell of the water electrolysis device, but when the oxygen humidity is high, the hydrogen content is high, and the flow rate is too high, the dehydrogenation device cannot completely remove the hydrogen, and the external dehydrogenation device is not beneficial to system simplification.
Disclosure of Invention
In view of the defects of the prior art, the embodiments of the present application provide an electrolytic water film electrode, a method for preparing the same, and a hydrogen production apparatus, which are improved for membrane electrode to achieve dehydrogenation, thereby increasing the purity of oxygen on the anode side and the purity of hydrogen on the cathode side.
In a first aspect, an embodiment of the present application provides an electrolytic water film electrode, which includes a cathode catalyst layer, a proton exchange membrane, a dehydrogenation catalyst layer, and an anode catalyst layer stacked in sequence. Wherein, the catalyst in the dehydrogenation catalyst layer comprises a substance containing at least one element of Pt and Pd elements.
When hydrogen enters the anode side of the proton exchange membrane through the proton exchange membrane, the hydrogen first contacts with the dehydrogenation catalyst layer on the anode side (the dehydrogenation catalyst layer is positioned on the anode side of the proton exchange membrane and contacts with the proton exchange membrane), the hydrogen is converted into hydrogen ions through the catalyst in the dehydrogenation catalyst layer, meanwhile, a part of oxygen generated on the anode side is diffused into the dehydrogenation catalyst layer 130, and the catalyst in the dehydrogenation catalyst layer can also convert the oxygen diffused into the dehydrogenation catalyst layer into O2-Allowing hydrogen ions and O2-The reaction produces water. Therefore, the catalyst in the dehydrogenation catalyst layer is a substance containing at least one of Pt and Pd elements, so that the functions of hydrogen oxidation and oxygen reduction can be met, the hydrogen and the oxygen react to obtain water, the purpose of dehydrogenation on the anode side is achieved, and the purity of the oxygen on the anode side is improved; at the same time, the amount of oxygen diffusing to the cathode side of the anode side can be reduced (even eliminated), and the purity of the hydrogen on the cathode side is improved.
In some embodiments of the present application, the catalyst in the dehydrogenation catalyst layer includes at least one of Pt, pd, and alloys thereof.
In some embodiments of the present application, the catalyst in the cathode catalyst layer is a substance containing at least one of a noble metal element and a transition metal element.
In some embodiments of the present application, the noble metal element includes at least one of Pt, pd, and Au elements.
In some embodiments of the present application, the noble metal includes at least one of elemental Pt, elemental Pd, elemental Au, and alloys thereof.
In some embodiments of the present application, the transition metal element includes at least one element selected from Fe, co, ni, cu, mo, and W.
In some embodiments of the present application, the transition metal includes at least one of elemental Fe, elemental Co, elemental Ni, elemental Cu, elemental Mo, elemental W, and alloys thereof, sulfide, selenide, carbide, nitride, and phosphide.
In some embodiments of the present application, the catalyst in the anode catalyst layer is a material containing at least one element selected from Ir and Ru.
In some embodiments of the present application, the catalyst in the anode catalyst layer includes at least one of elemental Ir, elemental Ru, alloys thereof, and oxides thereof.
In some embodiments of the present application, the proton exchange membrane is selected from one of a perfluorosulfonic acid polymer type proton exchange membrane, a modified proton exchange membrane, and an enhanced proton exchange membrane.
In some embodiments of the present application, the thickness ratio of the cathode catalyst layer, the proton exchange membrane, the dehydrogenation catalyst layer, and the anode catalyst layer is (10-100): (30-200): (5-20): (10-100), and the thickness of the electrolytic water film electrode is 50-500 μm.
In a second aspect, an embodiment of the present application provides a method for preparing the above electrolytic water film electrode, including: and forming a cathode catalyst layer on the first surface of the proton exchange membrane. And forming a dehydrogenation catalyst layer on the second surface of the proton exchange membrane, wherein the catalyst in the dehydrogenation catalyst layer is a substance containing at least one element of Pt and Pd elements. And forming an anode catalyst layer on the surface of the dehydrogenation catalyst layer.
The preparation method is simple, a dehydrogenation catalyst layer is formed on the anode side of the proton exchange membrane, when hydrogen passes through the proton exchange membrane and enters the anode side of the proton exchange membrane, the hydrogen firstly contacts with the dehydrogenation catalyst layer on the anode side (the dehydrogenation catalyst layer is positioned on the anode side of the proton exchange membrane and contacts with the proton exchange membrane), the hydrogen is converted into hydrogen ions through the catalyst in the dehydrogenation catalyst layer, meanwhile, a part of oxygen generated on the anode side is diffused into the dehydrogenation catalyst layer 130, and the catalyst in the dehydrogenation catalyst layer can also convert the oxygen diffused into the dehydrogenation catalyst layer into O2-Allowing hydrogen ions and O2-The reaction produces water. Thereby achieving the purpose of hydrogen elimination on the anode side and improving the purity of oxygen on the anode side; at the same time, the amount of oxygen diffusing to the cathode side on the anode side is reduced (or even eliminated) to improve the purity of the hydrogen on the cathode side.
In some embodiments of the present application, a cathode catalyst slurry is sprayed or transferred onto a first surface of a proton exchange membrane to form a cathode catalyst layer; spraying or transferring the dehydrogenation catalyst slurry on the second surface of the proton exchange membrane to form a dehydrogenation catalyst layer; and spraying or transferring anode catalyst slurry on the surface of the dehydrogenation catalyst layer to form an anode catalyst layer.
In a third aspect, an embodiment of the present application provides a hydrogen production device, including the above-mentioned electrolytic water film electrode.
The hydrogen and the oxygen on the anode side can react to obtain water, so that the aim of hydrogen elimination on the anode side is fulfilled, and the purity of the oxygen on the anode side is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a schematic layer structure diagram of an electrolytic water film electrode according to an embodiment of the present application.
Icon: 110-a cathode catalyst layer; 120-a proton exchange membrane; 130-a dehydrogenation catalyst layer; 140-anode catalyst layer.
Detailed Description
In the prior art, besides adding a dehydrogenation device for external dehydrogenation, internal dehydrogenation can be performed, wherein the method can be as follows: hydrogen and oxygen recombination is catalyzed by depositing platinum particles inside the proton exchange membrane. However, in order to deposit platinum particles on the inside of the proton exchange membrane, the proton exchange membrane needs to be pretreated so that the platinum particles are deposited on the inside of the proton exchange membrane. However, the pretreatment method of the proton exchange membrane is complicated, consumes more platinum metal, is not economical, and the platinum loading capacity obtained by pretreatment is not easy to control, thereby being not beneficial to the simplification of the production process.
Therefore, the present application provides an electrolytic water membrane electrode, which forms a single dehydrogenation catalyst layer 130 for dehydrogenation, without depositing platinum particles inside the proton exchange membrane 120.
Fig. 1 is a schematic layer structure diagram of an electrolytic water film electrode according to an embodiment of the present application. Referring to fig. 1, in the present application, the electrolytic water membrane electrode includes a cathode catalyst layer 110, a proton exchange membrane 120, a dehydrogenation catalyst layer 130, and an anode catalyst layer 140, which are sequentially stacked. The catalyst in the dehydrogenation catalyst layer 130 is a substance containing at least one of Pt and Pd elements.
When hydrogen passes from the cathode side to the anode side through the proton exchange membrane 120, it first reacts withThe hydrogen elimination catalyst layer 130 on the anode side is in contact with each other, hydrogen is converted into hydrogen ions by the catalyst in the hydrogen elimination catalyst layer 130, and at the same time, a part of oxygen generated on the anode side is diffused into the hydrogen elimination catalyst layer 130, and the catalyst in the hydrogen elimination catalyst layer 130 can also convert oxygen diffused into the hydrogen elimination catalyst layer 130 into O2-Hydrogen ion and O2-The reaction produces water. Therefore, the catalyst in the dehydrogenation catalyst layer 130 is a substance containing at least one of Pt and Pd elements, so that the functions of hydrogen oxidation and oxygen reduction can be satisfied, so that hydrogen and oxygen react to obtain water, thereby achieving the purpose of dehydrogenation on the anode side and improving the purity of oxygen on the anode side; and meanwhile, the amount of oxygen diffused to the cathode at the anode side can be reduced (even eliminated), and the purity of hydrogen at the cathode side is improved.
Optionally, the catalyst in the dehydrogenation catalyst layer 130 includes at least one of Pt, pd, and alloys thereof. For example: the catalyst in the dehydrogenation catalyst layer 130 is one or more of a simple substance of Pt, a simple substance of Pd, a Pt alloy and a Pd alloy.
Alternatively, the catalyst in the cathode catalyst layer 110 is a substance containing at least one of a noble metal element and a transition metal element. The catalyst in the cathode catalyst layer 110 may contain a noble metal element, or a transition metal element, or both a noble metal element and a transition metal element.
Wherein the noble metal element comprises at least one element of Pt, pd and Au elements. Optionally, the noble metal comprises at least one of Pt, pd, au, and alloys thereof. For example: the noble metal is one or more of a Pt simple substance, a Pd simple substance, an Au simple substance, a Pt alloy, a Pd alloy and an Au alloy.
Wherein the transition metal element comprises at least one element of Fe, co, ni, cu, mo and W elements. Optionally, the transition metal includes at least one of a simple substance of Fe, a simple substance of Co, a simple substance of Ni, a simple substance of Cu, a simple substance of Mo, a simple substance of W and an alloy thereof, a sulfide, a selenide, a carbide, a nitride, and a phosphide. For example: the transition metal is one or more of Fe simple substance, co simple substance, ni simple substance, cu simple substance, mo simple substance, W simple substance, fe alloy, co alloy, ni alloy, cu alloy, mo alloy, W alloy, sulfide, selenide, carbide, nitride and phosphide of the transition metal.
In the present application, the catalyst in the anode catalyst layer 140 is a substance containing at least one element of Ir and Ru. Alternatively, the catalyst in the anode catalyst layer 140 includes at least one of an Ir simple substance, a Ru simple substance, an alloy thereof, and an oxide thereof. For example: the catalyst in the anode catalyst layer 140 is one or more of an Ir simple substance, a Ru simple substance, an Ir alloy, a Ru alloy, an Ir oxide, and a Ru oxide.
The catalyst mainly means a substance component containing an active metal element, and the catalyst further includes a carrier on which the substance component containing an active metal element is supported. The carrier may be carbon, oxide, etc., and the present application is not limited as long as the carrier can carry the metal active ingredient, and is within the scope of the present application.
In the present application, the proton exchange membrane 120 is selected from one of a perfluorosulfonic acid polymer type proton exchange membrane 120, a modified proton exchange membrane 120, and an enhanced proton exchange membrane 120. For the enhanced proton exchange membrane 120, the pressure difference resistance of the membrane electrode can be improved, and the service life of the membrane electrode is prolonged; and the thickness of the electrolytic solution is relatively thin, so that the internal resistance of the film can be reduced, and the electrolytic efficiency can be improved.
In the present application, the thickness ratio of the cathode catalyst layer 110, the proton exchange membrane 120, the dehydrogenation catalyst layer 130, and the anode catalyst layer 140 is (10-100): 30-200): 5-20: (10-100), and the thickness of the electrolytic water film electrode is 50-500 μm. The thickness is matched, so that the membrane electrode can electrolyze water more efficiently.
Illustratively, the thickness of the electrolytic water film electrode is 50-150 μm, 150-250 μm, 250-350 μm, 350-450 μm, or 450-500 μm.
The preparation method of the electrolytic water film electrode comprises the following steps: a cathode catalyst layer 110 is formed on a first surface of the proton exchange membrane 120. A dehydrogenation catalyst layer 130 is formed on the second surface of the proton exchange membrane 120, wherein the catalyst in the dehydrogenation catalyst layer 130 is a substance containing at least one of the above-mentioned Pt and Pd elements. An anode catalyst layer 140 is formed on the surface of the dehydrogenation catalyst layer 130.
The preparation method is simple, a dehydrogenation catalyst layer 130 is formed on the anode side of the proton exchange membrane 120, when hydrogen passes through the proton exchange membrane 120 from the cathode side and enters the anode side, the hydrogen is firstly contacted with the dehydrogenation catalyst layer 130 on the anode side, the hydrogen is converted into hydrogen ions through the catalyst in the dehydrogenation catalyst layer 130, meanwhile, a part of oxygen generated on the anode side is diffused into the dehydrogenation catalyst layer 130, and the catalyst in the dehydrogenation catalyst layer 130 can also convert the oxygen diffused into the dehydrogenation catalyst layer 130 into O2-Hydrogen ion and O2-The reaction produces water. Thereby achieving the purpose of hydrogen elimination on the anode side and improving the purity of oxygen on the anode side; at the same time, the amount of oxygen diffusing to the cathode side on the anode side is reduced (or even eliminated) to improve the purity of the hydrogen on the cathode side.
Embodiments of the present disclosure include spraying or transferring a cathode catalyst slurry on a first surface of the proton exchange membrane 120 to form a cathode catalyst layer 110; spraying or transferring the dehydrogenation catalyst slurry on the second surface of the proton exchange membrane 120 to form a dehydrogenation catalyst layer 130; the anode catalyst layer 140 is formed by spraying or transferring anode catalyst paste on the surface of the dehydrogenation catalyst layer 130.
The catalyst layer structures on the cathode side and the anode side can be formed by spraying; the catalyst layer structures on the cathode side and the anode side can be formed by transfer printing; the catalyst layer on the cathode side can be formed by spraying, and the catalyst layer on the anode side can be formed by transfer printing; the catalyst layer on the anode side may be formed by spraying, and the catalyst layer on the cathode side may be formed by transfer; the hydrogen elimination catalyst layer 130 can be formed by spraying and the anode catalyst layer 140 can be formed by transfer printing; the dehydrogenation catalyst layer 130 may be formed by transfer printing, the anode catalyst layer 140 may be formed by spray coating, or the like; the present application is not limited.
Wherein the cathode catalyst slurry comprises a cathode catalyst (the cathode catalyst comprises a carrier and a component containing an active metal element substance supported on the carrier) and a resin solution, and the mass ratio of the cathode catalyst to the resin solution is (10-40) to (10-300).
The hydrogen-eliminating catalyst slurry comprises a hydrogen-eliminating catalyst (the hydrogen-eliminating catalyst comprises a carrier and a component containing an active metal element substance loaded on the carrier) and a resin solution, and the mass ratio of the hydrogen-eliminating catalyst to the resin solution is (10-40) to (10-300).
The anode catalyst slurry comprises an anode catalyst (the anode catalyst comprises a component of an active metal element-containing substance or a component of an active metal element-containing substance supported on a carrier) and a resin solution, and the mass ratio of the anode catalyst to the resin solution is (10-40): (10-300).
The electrolytic water film electrode can be used for preparing a hydrogen production device, and can enable hydrogen and oxygen on the anode side to react to obtain water, so that the aim of hydrogen elimination on the anode side is fulfilled, and the purity of oxygen on the anode side is improved.
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of an electrolytic water film electrode, which comprises the following steps:
(1) Mixing iridium oxide and Nafion solution in a mass ratio of 30.
(2) And mixing the carbon-supported platinum catalyst with the mass ratio of 30.
(3) And mixing the carbon-supported platinum catalyst with the mass ratio of 30.
(4) Spraying the cathode catalyst slurry obtained in the step (3) on the cathode side of the Nafion117 proton exchange membrane with the thickness of 178 mu m, and drying to obtain a cathode catalyst layer with the thickness of 50 mu m; spraying the hydrogen elimination catalyst slurry obtained in the step (2) on the anode side of the Nafion117 proton exchange membrane, and drying to obtain a hydrogen elimination catalyst layer with the thickness of 10 microns; and (3) spraying the anode catalyst slurry obtained in the step (1) on the surface of the dehydrogenation catalyst layer, and drying to obtain an anode catalyst layer with the thickness of 100 microns, thereby finally obtaining the electrolytic water film electrode.
Example 2
Example 2 is a modification of example 1, and example 2 differs from example 1 in that: the Nafion117 proton exchange membrane with a thickness of 178 μm was replaced by an enhanced proton exchange membrane with a thickness of 90 μm.
Example 3
Example 3 is a modification of example 1, and example 3 differs from example 1 in that: in the step (4), coating the cathode catalyst slurry obtained in the step (3) on the surface of the PET protective film, drying to obtain a cathode catalyst layer with the thickness of 50 microns, and transferring the cathode catalyst layer to the cathode side of the Nafion117 proton exchange membrane; coating the hydrogen elimination catalyst slurry obtained in the step (2) on the surface of the PET protective film, drying to obtain a hydrogen elimination catalyst layer with the thickness of 10 mu m, and transferring the hydrogen elimination catalyst layer to the anode side of the Nafion117 proton exchange membrane; and (3) coating the anode catalyst slurry obtained in the step (1) on the surface of the PET protective film, drying to obtain an anode catalyst layer with the thickness of 100 microns, and transferring the anode catalyst layer to the surface of the dehydrogenation catalyst layer to finally obtain the electrolytic water film electrode.
Example 4
Example 4 is a modification of example 1, and example 4 differs from example 1 in that: in the active components of the dehydrogenation catalyst, the carbon-supported platinum catalyst is replaced by a carbon-supported palladium catalyst.
Example 5
Example 5 is a modification of example 1, and example 5 differs from example 1 in that: in the active components in the dehydrogenation catalyst, a carbon-supported platinum catalyst is replaced by a carbon-supported platinum-palladium alloy catalyst (the molar ratio of platinum element to palladium element in the platinum-palladium alloy is 1.
Example 6
Example 6 is a modification of example 1, and example 6 differs from example 1 in that: in the active components in the dehydrogenation catalyst, the carbon-supported platinum catalyst is replaced by a mixture of a carbon-supported platinum catalyst and a carbon-supported palladium catalyst (the mass ratio of the carbon-supported platinum catalyst to the carbon-supported palladium catalyst is 1.
Comparative example 1
The embodiment provides a preparation method of an electrolytic water film electrode, which comprises the following steps:
(1) And mixing the iridium oxide and the Nafion solution in a mass ratio of 30.
(2) And mixing the carbon-supported platinum catalyst and the Nafion solution in a mass ratio of 30.
(3) Spraying the cathode catalyst slurry in the step (2) on the cathode side of the Nafion117 proton exchange membrane with the thickness of 178 mu m, and drying to obtain a cathode catalyst layer with the thickness of 50 mu m; and (2) spraying the anode catalyst slurry obtained in the step (1) on the anode side of the Nafion117 proton exchange membrane, and drying to obtain an anode catalyst layer with the thickness of 100 microns, thereby finally obtaining the electrolytic water membrane electrode.
Comparative example 2
Comparative example 2 is an improvement over comparative example 1, and comparative example 2 differs from comparative example 1 in that: the Nafion117 proton exchange membrane with the thickness of 178 μm is replaced by an enhanced proton exchange membrane with the thickness of 90 μm.
Experimental example 1
The electrolytic water membrane electrodes provided in examples 1 to 6 and comparative examples 1 to 2 were assembled into a water electrolytic cell, and an anode current collecting plate, an anode gas diffusion layer, a membrane electrode, a cathode gas diffusion layer, and a cathode current collecting plate were assembled into a water electrolytic cell in order, and it was ensured that the cathode and anode catalyst layers of the membrane electrode were in close contact with the cathode and anode gas diffusion layers, respectively. The water electrolysis cell was subjected to constant current electrolysis in a two-way water supply mode to produce gas, and the purity of the hydrogen on the cathode side and the purity of the oxygen on the anode side were respectively detected by a gas chromatograph, to obtain table 1.
TABLE 1 Anode side oxygen purity and cathode side hydrogen purity values for membrane electrodes
Figure BDA0003094957340000101
Figure BDA0003094957340000111
As can be seen from table 1, the membrane electrodes provided in examples 1 to 6 have a good dehydrogenation effect, and can improve the purity of oxygen on the anode side and the purity of hydrogen on the cathode side.
Comparing example 1 with example 2, it can be seen that the effect of the dehydrogenation catalyst layer on improving the gas purity is equally obvious no matter the Nafion117 proton exchange membrane or the enhanced proton exchange membrane is adopted.
Comparing example 1 with example 3, it can be seen that the effect of the dehydrogenation catalyst layer on improving the gas purity is equally obvious whether spray coating or transfer printing process is adopted.
The comparison between example 1 and examples 4-6 shows that the effect of the dehydrogenation catalyst layer on the improvement of the gas purity is equally significant regardless of which dehydrogenation catalyst is used.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (6)

1. An electrolytic water film electrode is characterized by comprising a cathode catalyst layer, a proton exchange membrane, a dehydrogenation catalyst layer and an anode catalyst layer which are sequentially stacked;
wherein the catalyst in the dehydrogenation catalyst layer is at least one of a carbon-supported platinum catalyst, a carbon-supported palladium catalyst and a carbon-supported platinum-palladium alloy catalyst;
the catalyst in the anode catalyst layer is at least one of Ir simple substance, ru simple substance, alloy thereof and oxide thereof;
the catalyst in the cathode catalyst layer is a substance containing at least one element of a noble metal element and a transition metal element, and the catalyst containing the noble metal element in the cathode catalyst layer is a carbon-supported platinum catalyst.
2. The electrolytic water film electrode according to claim 1, wherein the transition metal element is at least one element selected from Fe, co, ni, cu, mo, W;
or/and the substance containing the transition metal element is at least one of Fe simple substance, co simple substance, ni simple substance, cu simple substance, mo simple substance, W simple substance and alloy thereof, sulfide, selenide, carbide, nitride and phosphide.
3. The electrolytic water membrane electrode according to any one of claims 1 to 2, wherein the proton exchange membrane is selected from one of a perfluorosulfonic acid polymer type proton exchange membrane, a modified proton exchange membrane, and an enhanced proton exchange membrane;
or/and the thickness ratio of the cathode catalyst layer, the proton exchange membrane, the dehydrogenation catalyst layer and the anode catalyst layer is (10-100): 30-200): 5-20: (10-100), and the thickness of the electrolytic water membrane electrode is 50-500 μm.
4. A method for preparing an electrolytic water film electrode according to any one of claims 1 to 3, comprising:
forming the cathode catalyst layer on the first surface of the proton exchange membrane;
forming the dehydrogenation catalyst layer on the second surface of the proton exchange membrane;
and forming the anode catalyst layer on the surface of the dehydrogenation catalyst layer.
5. The preparation method according to claim 4, wherein the cathode catalyst layer is formed by spraying or transferring a cathode catalyst slurry on the first surface of the proton exchange membrane; spraying or transferring dehydrogenation catalyst slurry on the second surface of the proton exchange membrane to form the dehydrogenation catalyst layer; and spraying or transferring anode catalyst slurry on the surface of the dehydrogenation catalyst layer to form the anode catalyst layer.
6. A hydrogen production apparatus comprising the electrolytic water film electrode according to any one of claims 1 to 3.
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