CN116575068A - Catalytic layer slurry, preparation method thereof, membrane electrode and electrochemical hydrogen compressor - Google Patents

Catalytic layer slurry, preparation method thereof, membrane electrode and electrochemical hydrogen compressor Download PDF

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CN116575068A
CN116575068A CN202310392697.0A CN202310392697A CN116575068A CN 116575068 A CN116575068 A CN 116575068A CN 202310392697 A CN202310392697 A CN 202310392697A CN 116575068 A CN116575068 A CN 116575068A
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catalytic layer
layer slurry
membrane electrode
ionomer
catalyst
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邹杰鑫
王旻
王海江
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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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
    • C25B11/04—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
    • 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
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • 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
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The application relates to the technical field of energy batteries, in particular to a catalytic layer slurry, a preparation method thereof, a membrane electrode and an electrochemical hydrogen compressor. The catalyst layer slurry for the electrochemical hydrogen compressor comprises the following components in parts by weight: 0.02-0.20 part of platinum carbon catalyst, 0.005-0.05 part of ionomer, 0.3-0.5 part of alcohol solvent and 0.3-0.5 part of water solvent; wherein the mass ratio of the water solvent to the alcohol solvent is (0.6-1.2): 1, the mass ratio of the ionomer to the carbon in the platinum-carbon catalyst is (0.9-1.5): 1. the anode catalytic layer of the membrane electrode for preparing the electrochemical hydrogen compressor has a good porous structure and more catalytic active sites on a microscopic level, and meanwhile, the membrane electrode containing the anode catalytic layer has good hydrogen compression performance and low electrochemical impedance performance, so that the anode catalytic layer is well applicable to the running environment of the electrochemical hydrogen compressor.

Description

Catalytic layer slurry, preparation method thereof, membrane electrode and electrochemical hydrogen compressor
Technical Field
The application belongs to the technical field of energy batteries, and particularly relates to a catalytic layer slurry, a preparation method thereof, a membrane electrode and an electrochemical hydrogen compressor.
Background
An Electrochemical Hydrogen Compressor (EHC) is a device capable of converting electric energy into compression energy through electrochemical reaction, and is capable of realizing pressurization through oxidation-reduction reaction, low-pressure hydrogen generates protons through oxidation reaction at an anode, the protons are transferred to a cathode through a proton exchange membrane and then reduced into hydrogen, and back pressure can be generated by the cathode hydrogen under the driving of an external voltage.
The Membrane Electrode (MEA) is a core component of an electrochemical hydrogen compressor and mainly comprises a proton exchange membrane, a catalytic layer and a gas diffusion layer. The catalytic layer in the membrane electrode is the main place for the electrochemical reaction to proceed, wherein the anode catalytic layer generates Hydrogen Oxidation Reaction (HOR), and the cathode catalytic layer generates Hydrogen Evolution Reaction (HER). The three-phase interface and spatial configuration in the catalytic layer are usually formed by catalytic layer slurry, however, the performance of the catalytic layer prepared by the catalytic layer slurry of the existing electrochemical hydrogen compressor is still to be improved, and the formula of the related catalytic layer slurry is not clear.
Disclosure of Invention
The application aims to provide a catalytic layer slurry, a preparation method thereof, a membrane electrode and an electrochemical hydrogen compressor, and aims to solve the technical problem of how to improve the performance of a catalytic layer of the electrochemical hydrogen compressor.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, an embodiment of the present application provides a catalytic layer slurry for an electrochemical hydrogen compressor, including the following components in parts by weight:
wherein the mass ratio of the water solvent to the alcohol solvent is (0.6-1.2): 1, the mass ratio of the ionomer to the carbon in the platinum-carbon catalyst is (0.9-1.5): 1.
in one embodiment, the mass ratio of carbon in the ionomer to the platinum carbon catalyst is (0.9 to 1.2): 1.
in one embodiment, the platinum carbon catalyst has a platinum loading of 20 to 70wt%.
In one embodiment, the ionomer comprises at least one of a perfluorosulfonic acid resin and a perfluorosulfonic acid resin derivative.
In one embodiment, the alcohol solvent includes at least one of methanol, ethanol, propanol, and butanol.
In a second aspect, an embodiment of the present application provides a method for preparing a catalytic layer slurry, including the steps of:
providing all raw material components in the catalytic layer slurry of the embodiment of the application;
and mixing the platinum carbon catalyst, the ionomer, the alcohol solvent and the water solvent to obtain the catalyst layer slurry.
In one embodiment, the mixing treatment comprises mixing using at least one of ball milling, homogenization, sonication, and stirring.
In a third aspect, an embodiment of the present application provides a membrane electrode, including a proton exchange membrane, and an anode catalytic layer and a cathode catalytic layer disposed on two sides of the proton exchange membrane, where the anode catalytic layer is made from the catalytic layer slurry in the embodiment of the present application and/or the catalytic layer slurry prepared by the preparation method in the embodiment of the present application.
In one embodiment, the anode catalytic layer has a thickness of 10 to 50 μm.
In a fourth aspect, an embodiment of the present application provides an electrochemical hydrogen compressor comprising a membrane electrode according to an embodiment of the present application.
The catalyst layer slurry for the electrochemical hydrogen compressor provided by the embodiment of the application contains platinum-carbon catalyst, ionomer, alcohol solvent and water solvent with specific weight components, and the catalyst layer slurry is used for preparing the membrane electrode anode catalyst layer of the electrochemical hydrogen compressor, so that the obtained anode catalyst layer has a good porous structure and more catalytic active sites on a microscopic level, and meanwhile, the membrane electrode containing the anode catalyst layer has good hydrogen compression performance and low electrochemical impedance performance, therefore, the catalyst layer slurry provided by the embodiment of the application can be well applied to the operation environment of the electrochemical hydrogen compressor and has good application prospect in the electrochemical hydrogen compressor.
According to the preparation method of the catalytic layer slurry provided by the second aspect of the embodiment of the application, the platinum-carbon catalyst, the ionomer, the alcohol solvent and the water solvent of all raw material components in the catalytic layer slurry are mixed and treated to obtain the catalytic layer slurry. The preparation method is simple in process, and the obtained catalyst layer slurry can be used for preparing the membrane electrode anode catalyst layer of the electrochemical hydrogen compressor, so that the catalyst layer slurry is well applicable to the running environment of the electrochemical hydrogen compressor.
The membrane electrode provided by the third aspect of the embodiment of the application comprises a proton exchange membrane, and an anode catalytic layer and a cathode catalytic layer which are respectively arranged on two sides of the proton exchange membrane, and is prepared from the catalytic layer slurry prepared by the catalytic layer slurry and/or the catalytic layer slurry prepared by the preparation method of the embodiment of the application, so that the catalytic activity of the anode catalytic layer of the membrane electrode is good, and the membrane electrode has good hydrogen compression performance and low electrochemical impedance performance, therefore, the membrane electrode has good application prospect in an electrochemical hydrogen compressor.
The electrochemical hydrogen compressor provided by the fourth aspect of the embodiment of the application comprises the membrane electrode special for the embodiment of the application, so that the electrochemical hydrogen compressor can well convert electric energy into compression energy and has the characteristics of good stability and high efficiency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 shows that the mass ratio of the ionomer to the platinum carbon catalyst provided in the embodiment of the application is 0.9:1, a transmission electron microscope image after the catalytic layer slurry is prepared into a catalytic layer;
FIG. 2 is a scanning electron microscope image of a catalyst layer made of catalyst layer slurry of ionomer and Pt-C catalyst with different mass ratios according to the embodiment of the present application;
FIG. 3 is a graph showing hydrogen compression performance of a membrane electrode after a catalyst layer is made from catalyst layer slurry of ionomer and Pt-C catalyst in different mass ratios according to an embodiment of the present application;
fig. 4 is a graph of electrochemical impedance of a membrane electrode after a catalyst layer is made from catalyst layer slurry of ionomer and platinum carbon catalyst of different mass ratios according to an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s).
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
The first aspect of the embodiment of the application provides a catalytic layer slurry of an electrochemical hydrogen compressor, which comprises the following components in parts by weight:
wherein the mass ratio of the water solvent to the alcohol solvent is (0.6-1.2): 1, the mass ratio of the ionomer to the carbon in the platinum-carbon catalyst is (0.9-1.5): 1.
the membrane electrode is a core component of the proton exchange membrane electrochemical hydrogen compressor, and cathode reaction, anode reaction and electronic conduction and ion conduction in the electrochemical reaction process all occur on the membrane electrode; and the preparation of the catalytic layer of the membrane electrode determines the performance of the proton exchange membrane electrochemical hydrogen compressor to a certain extent. Therefore, the catalyst layer slurry provided by the embodiment of the application contains the platinum-carbon catalyst, the ionomer, the alcohol solvent and the water solvent with specific weight components, and the catalyst layer slurry is used for preparing the membrane electrode anode catalyst layer of the electrochemical hydrogen compressor, so that the obtained anode catalyst layer has a good porous structure and more catalytic active sites on a microscopic level, and meanwhile, the membrane electrode containing the anode catalyst layer has good hydrogen compression performance and low electrochemical impedance performance. Therefore, the catalyst layer slurry provided by the embodiment of the application can be well applied to the running environment of the electrochemical hydrogen compressor, and has a good application prospect in the electrochemical hydrogen compressor.
Specifically, the platinum-carbon (Pt/C) catalyst in the catalyst layer slurry is a carrier catalyst for supporting platinum on activated carbon, and is used in the anode catalyst layer of the membrane electrode to mainly catalyze the hydrogen oxidation. Ionomer (Ionomer) refers to a polymer containing ionic groups in the hydrocarbon molecular chain that can form a crosslinked network through ionic interactions, thereby allowing the anode catalytic layer to have a continuous proton conducting network. The platinum-carbon catalyst and the ionomer are dispersed in the mixed solvent of the alcohol solvent and the water solvent under the condition of the component proportion, so that the uniformly dispersed catalyst layer slurry can be formed, the viscosity of the catalyst layer slurry is proper, the catalyst layer slurry can be suitable for different film forming processes such as knife coating, spraying, screen printing and the like, the obtained anode catalyst layer has a good porous structure, has more catalytic active sites on a microscopic level, and simultaneously has good hydrogen compression performance and low electrochemical impedance performance.
Specifically, the catalyst layer slurry may contain 0.02 to 0.20 parts of a platinum carbon catalyst, for example, 0.02 parts, 0.04 parts, 0.08 parts, 0.10 parts, 0.12 parts, 0.14 parts, 0.18 parts, 0.20 parts, and the like. The ionomer may be 0.005 to 0.05 parts, for example, 0.005 parts, 0.008 parts, 0.01 parts, 0.015 parts, 0.02 parts, 0.025 parts, 0.03 parts, 0.04 parts, 0.045 parts, 0.05 parts, etc. The alcohol solvent may be 0.3 to 0.5 parts, for example, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, or 0.5 parts. The water solvent may be 0.3 to 0.5 parts, for example, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.47 parts, or 0.5 parts. The catalyst layer slurry prepared from the platinum-carbon catalyst, the ionomer, the alcohol solvent and the water solvent by weight is used for preparing the membrane electrode anode catalyst layer of the electrochemical hydrogen compressor, so that the obtained anode catalyst layer has a good porous structure and more catalytic active sites on a microscopic level, and meanwhile, the membrane electrode containing the anode catalyst layer has good hydrogen compression performance and low electrochemical impedance performance.
In one embodiment, the mass ratio of ionomer to carbon in the platinum carbon catalyst in the catalytic layer slurry is (0.9-1.5): 1. for example, the mass ratio of carbon in the ionomer and the platinum carbon catalyst is expressed as I/C, which may be 0.9, 1.0, 1.2, 1.4, 1.5, etc. The anode catalytic layer is prepared from the catalytic layer slurry with the I/C=0.9-1.5, so that the membrane electrode has good hydrogen compression performance and low electrochemical impedance performance, and can be suitable for environments with different humidity. Still further, I/c=0.9 to 1.2.
In one embodiment, the platinum carbon catalyst has a platinum loading of 20 to 70wt%. For example, it may be 20wt.% Pt/C, 25wt.% Pt/C, 30wt.% Pt/C, 35wt.% Pt/C, 40wt.% Pt/C, 50wt.% Pt/C, 60wt.% Pt/C, 70wt.% Pt/C, and so forth. The catalyst with the platinum loading has good catalytic effect.
In one embodiment, the ionomer comprises at least one of a perfluorosulfonic acid resin and a perfluorosulfonic acid resin derivative. Specifically, it may be a long-side-chain perfluorosulfonic acid resin or a short-side-chain perfluorosulfonic acid resin.
In one embodiment, the ionomer is prepared as a slurry of the catalytic layer in the form of a solution, for example, perfluorosulfonic acid resin, and specifically, may be Nafion solution, aquivion solution, 3M solution, etc., with a mass concentration ranging from about 5 to 30%, and finally 0.005 to 0.05 parts by weight of the ionomer.
In one embodiment, the mass ratio of the aqueous solvent to the alcoholic solvent in the catalyst layer slurry is (0.6-1.2): 1, for example, the mass ratio of aqueous solvent to alcoholic solvent may be 0.6: 1. 0.8: 1. 1:1. 1:1.2, etc. The mixed solvent formed by the water solvent and the alcohol solvent in the proportion range can well disperse the ionomer and the platinum carbon catalyst.
In one embodiment, the alcohol solvent includes at least one of methanol, ethanol, propanol, and butanol.
The second aspect of the embodiment of the application provides a preparation method of a catalyst layer slurry, which comprises the following steps:
s01: providing all raw material components in the catalytic layer slurry of the embodiment of the application;
s02: and mixing the platinum carbon catalyst, the ionomer, the alcohol solvent and the water solvent to obtain the catalyst layer slurry.
According to the preparation method of the catalytic layer slurry provided by the embodiment of the application, the platinum-carbon catalyst, the ionomer, the alcohol solvent and the water solvent of all raw material components in the catalytic layer slurry are mixed and treated to obtain the catalytic layer slurry. The preparation method is simple in process, and the obtained catalyst layer slurry can be used for preparing the membrane electrode anode catalyst layer of the electrochemical hydrogen compressor, so that the catalyst layer slurry is well applicable to the running environment of the electrochemical hydrogen compressor.
Step S01: a step of preparing raw materials.
Specific types and ratio ranges of the platinum carbon catalyst, the ionomer, the alcohol solvent and the aqueous solvent in each raw material component in the catalyst layer slurry are referred to above.
Step S02: the method is a raw material mixing treatment step.
In one embodiment, the mixing treatment comprises mixing using at least one of ball milling, homogenization, sonication, and stirring.
Specifically, taking a ball milling method as an example, the above-mentioned mixing treatment includes: the platinum carbon catalyst, ionomer, alcohol solvent and water solvent are charged into a ball mill tube in the desired ratio, and then grinding medium pellets are added. The ball milling tank is assembled on a ball milling instrument, and after the ball milling tank is well sealed, the running procedure is set as follows: forward rotation for 2-10 min, reverse rotation for 2-10 min, stopping for 2-10 min, rotating at 200-500 rpm and total running time for 5-200 h. And after the ball milling process is completed, obtaining the catalyst layer slurry. The ball milling method can lead the slurry of the catalytic layer to be uniformly mixed.
The third aspect of the embodiment of the application provides a membrane electrode, which comprises a proton exchange membrane, and an anode catalytic layer and a cathode catalytic layer which are respectively arranged at two sides of the proton exchange membrane, wherein the anode catalytic layer is prepared from the catalytic layer slurry of the embodiment of the application and/or the catalytic layer slurry prepared by the preparation method of the embodiment of the application.
The membrane electrode provided by the embodiment of the application comprises a proton exchange membrane, and an anode catalytic layer and a cathode catalytic layer which are respectively arranged at two sides of the proton exchange membrane, and is prepared from the catalytic layer slurry prepared by the catalytic layer slurry and/or the catalytic layer slurry prepared by the preparation method of the embodiment of the application, so that the catalytic activity of the anode catalytic layer of the membrane electrode is good, and the membrane electrode has good hydrogen compression performance and low electrochemical impedance performance, therefore, the membrane electrode has good application prospect in an electrochemical hydrogen compressor.
In an embodiment, the membrane electrode further includes a first gas diffusion layer and a second gas diffusion layer respectively disposed at two sides of the proton exchange membrane, wherein the first gas diffusion layer is located at a side of the anode catalytic layer away from the proton exchange membrane, and the second gas diffusion layer is located at a side of the cathode catalytic layer away from the proton exchange membrane. Thus, the membrane electrode consists of three parts, namely a proton exchange membrane (proton exchange membrane, PEM), a Catalytic Layer (CL) and a gas diffusion layer (gas diffusion layer, GDL), from inside to outside.
In one embodiment, the anode catalytic layer has a thickness of 10 to 50 μm. For example, the thickness of the anode catalytic layer may be 10 μm, 15 μm, 20 μm, 30 μm, 35 μm, 40 μm, 50 μm, or the like.
Specifically, the anode catalytic layer can be prepared by coating a proton exchange membrane. In the preparation process, the prepared catalyst layer slurry is coated on one side of a proton exchange membrane to form an anode catalyst coating membrane, and meanwhile, the cathode catalyst coating membrane can be further formed by coating the cathode catalyst layer slurry on the other side of the proton exchange membrane, and then a gas diffusion layer is hot-pressed on two sides of the catalyst coating membrane to form a membrane electrode.
Specifically, the anode catalytic layer can also be prepared by coating on gas diffusion. In the manufacturing process, the gas diffusion layer is used as a support body, the slurry of the catalytic layer is coated on the gas diffusion layer, and then the gas diffusion electrode is hot-pressed on two sides of the proton exchange membrane in a hot-pressing mode to form the membrane electrode.
Specifically, the anode catalytic layer can be prepared by a knife coating method, a spraying method and a screen printing method, the thickness of a knife coating wet film is set according to different solid contents in catalytic layer slurry, the specific wet film thickness can be 100-300 mu m, and then the anode catalytic layer with the thickness of 10-50 mu m is obtained after the anode catalytic layer is dried at room temperature (25 ℃ to 80 ℃) for 10-30 minutes.
According to a fourth aspect of the embodiment of the application, an electrochemical hydrogen compressor is provided, which comprises the membrane electrode according to the embodiment of the application.
The electrochemical hydrogen compressor provided by the embodiment of the application comprises the membrane electrode special for the embodiment of the application, so that the electrochemical hydrogen compressor can well convert electric energy into compression energy and has the characteristics of good stability and high efficiency.
The following description is made with reference to specific embodiments.
Example 1
A preparation method of the catalyst layer slurry comprises the following steps:
(1) Weighing the raw materials:
1000mg of a platinum carbon catalyst (commercial 50wt.% Pt/C, i.e. platinum content 500mg, carbon content 500 mg),
1500 The water content of the water in the water tank is the same as the water in the water tank,
1500 mg of n-propanol is added to the mixture,
2500mg ionomer solution (Nafion D2020 solution containing 450mg of perfluorosulfonic acid resin ionomer); i.e. the mass ratio of ionomer to carbon in the platinum carbon catalyst I/c=0.9.
(2) Mixing by ball milling: the platinum carbon catalyst, ionomer, alcohol solvent and water solvent weighed above were put into a ball mill tube, and then pellets were added. The ball milling tank is assembled on a ball milling instrument in a sealing way, and the operation procedure is set as follows: forward rotation for 5min, reverse rotation for 5min, stopping for 5min, rotating at 200-500 rpm and total running time of 10h. And after ball milling is completed, obtaining the catalyst layer slurry.
Example 2
A membrane electrode comprises a proton exchange membrane, an anode catalytic layer and a cathode catalytic layer which are respectively positioned at two sides of the proton exchange membrane, and a first gas diffusion layer positioned at one side of the anode catalytic layer far away from the proton exchange membrane, and a second gas diffusion layer positioned at one side of the cathode catalytic layer far away from the proton exchange membrane.
Wherein the proton exchange membrane material is Nafion XL, the cathode catalytic layer material is platinum-carbon catalyst loading 0.4mg/cm 2 The first gas diffusion layer and the second gas diffusion layer are made of carbon paper. The anode catalytic layer is prepared from the catalytic layer slurry in the embodiment 1, specifically, the prepared catalytic layer slurry is coated on the surface of a proton exchange membrane in a scraping way, and then the anode catalytic layer is obtained by drying for 10-30 min at 50 ℃.
Performance testing
Fig. 1 is a transmission electron microscope image of a catalyst layer slurry, specifically, a transmission electron microscope image of a catalyst layer slurry with I/c=0.9 in example 1, and it can be seen that the catalyst layer slurry is uniformly dispersed, and the elemental scanning shows that the ionomer and the Pt/C platinum carbon catalyst are uniformly distributed.
Fig. 2 is a scanning electron microscope image of an anode catalytic layer, specifically, the weight of the perfluorosulfonic acid resin ionomer of the catalytic layer slurry of I/c=0.9 in example 1 was replaced to form three groups of catalytic layer slurries of I/c=0.9, 1.2, 1.5, and the I/c=0.5 was used as a comparison. The results show that: the anode catalytic layer has poor void effect when I/c=0.5, while the anode catalytic layer has good uniform porous structure when I/c=0.9 to 1.5, and the pores are favorable for substance transmission in the anode catalytic layer, and the anode catalytic layer has better porous structure when I/c=0.9 to 1.2.
Fig. 3 is a graph of hydrogen compression performance of the membrane electrode of example 2 made of the respective corresponding catalytic layer slurries at I/c=0.5, 0.9, 1.2, 1.5, 1.8; the specific testing steps comprise: the test was carried out in an electrochemical clamp at 80℃and 100% RH.
The results show that: in the case of high humidity (relative humidity RH: 100%), the membrane electrode hydrogen compression performance was optimal at 0.9I/C, and only 64s was required for compression to 1MPa, and the membrane electrode having 1.2I/C required 108s for compression to 0.95MPa, however, the hydrogen compression performance was poor at 0.5 and 1.8I/C, as shown in FIG. 3 (a). As shown in fig. 3 (b), in the case of low humidity (relative humidity rh=50%), the membrane electrode has the most excellent hydrogen compression performance when I/C is 1.2, and 130s is required to compress hydrogen gas to 0.9MPa, and the membrane electrode compression performance corresponding to I/C of 1.5 and 0.9 is equivalent. Under low humidity conditions, more ionomer is needed in the catalytic layer to form a continuous proton conducting network due to the smaller ionomer volume.
From this, it can be seen that: the anode catalytic layer is manufactured when I/c=0.9-1.5, the corresponding membrane electrode has good hydrogen compression performance, and the hydrogen compression performance is better when I/c=0.9-1.2.
Fig. 4 is a graph of electrochemical impedance of the membrane electrode of example 2 made of the respective corresponding catalytic layer slurries at I/c=0.5, 0.9, 1.2, 1.5; the specific testing steps comprise: the test was carried out in an electrochemical clamp at 80 ℃.
The results show that: at I/c=1.5 and RH100%, the excess ionomer and excess moisture cause its own agglomeration, reducing the catalytic layer pore structure, and thus the mass transfer resistance starts to increase with further increase in I/C. And I/C is 1.2, the membrane electrode exhibits hydrogen compression performance at rh=50% comparable to that at rh=100%. The higher ionomer content is beneficial to improving the water retention performance of the catalytic layer under the low humidity condition, so that the proton conductivity of the catalytic layer is improved. Under low humidity condition (rh=50%) the ohmic resistance of its membrane electrode was 91.5mΩ·cm when the I/C ratio was 1.2 and 1.5, respectively 2 And 76.3mΩ·cm 2 Ohmic resistance of corresponding membrane electrode smaller than I/C=0.9 is 110.8mΩ·cm 2 . Thus, in drier environments, properly increasing the ionomer content in the catalytic layer is beneficial for reducing the ohmic resistance of the membrane electrode. However, excessive ionomer addition, such as when I/C > 1.5, may result in increased ohmic resistance and may also block the reactive sites, resulting in reduced overall hydrogen compression performance. While increasing the ionomer content in the range of I/c=0.9 to 1.2 under high humidity conditions (rh=100%) does not significantly change the membrane electrode ohmic resistance. This is due to the abundance of water in the catalytic layer at rh=100%, the ionomer reaching a critical level (I/c=1.2) being sufficient to form a continuous proton conducting network with an ohmic resistance of the membrane electrode of about 61mΩ·cm 2 This is significantly lower than the ohmic resistance of a membrane electrode at the same I/C ratio under low humidity conditions.
Therefore, considering the problem of anode drying of the electrochemical hydrogen compressor under the low humidity condition, the reasonable design of the catalytic layer is extremely critical, and the water absorption and compression performance of the catalytic layer can be effectively improved by properly increasing the ionomer content. The corresponding membrane electrode has good hydrogen compression performance and low ohmic resistance performance when I/c=0.9-1.5, and the performance is optimal when I/c=0.9-1.2.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims (10)

1. The catalytic layer slurry for the electrochemical hydrogen compressor is characterized by comprising the following components in parts by weight:
0.02-0.20 part of platinum-carbon catalyst
0.005 to 0.05 part of ionomer
Alcohol solvent 0.3-0.5 parts
0.3 to 0.5 part of water solvent
Wherein the mass ratio of the water solvent to the alcohol solvent is (0.6-1.2): 1, the mass ratio of carbon in the ionomer to the platinum carbon catalyst is (0.9-1.5): 1.
2. the catalytic layer slurry of claim 1, wherein the mass ratio of carbon in the ionomer and the platinum carbon catalyst is (0.9-1.2): 1.
3. the catalytic layer slurry of claim 1, wherein the platinum carbon catalyst has a platinum loading of 20 to 70wt%.
4. The catalytic layer slurry of claim 1, wherein the ionomer comprises at least one of a perfluorosulfonic acid resin and a perfluorosulfonic acid resin derivative.
5. The catalytic layer slurry of any of claims 1-4, wherein the alcoholic solvent comprises at least one of methanol, ethanol, propanol, and butanol.
6. The preparation method of the catalyst layer slurry is characterized by comprising the following steps:
providing each of the feedstock components in the catalytic layer slurry of any one of claims 1-5;
and mixing the platinum carbon catalyst, the ionomer, the alcohol solvent and the water solvent to obtain the catalytic layer slurry.
7. The method of preparing according to claim 6, wherein the mixing treatment comprises mixing by at least one of ball milling, homogenization, sonication, and stirring.
8. A membrane electrode comprising a proton exchange membrane and an anode catalytic layer and a cathode catalytic layer respectively arranged at two sides of the proton exchange membrane, wherein the anode catalytic layer is prepared from the catalytic layer slurry according to any one of claims 1 to 5 and/or the catalytic layer slurry prepared by the preparation method according to any one of claims 6 to 7.
9. The membrane electrode according to claim 8, wherein the anode catalytic layer has a thickness of 10 to 50 μm.
10. An electrochemical hydrogen compressor comprising the membrane electrode of claim 8 or 9.
CN202310392697.0A 2023-04-10 2023-04-10 Catalytic layer slurry, preparation method thereof, membrane electrode and electrochemical hydrogen compressor Pending CN116575068A (en)

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