CN114447347B - Fuel cell membrane electrode with low platinum loading and mass production and preparation method thereof - Google Patents
Fuel cell membrane electrode with low platinum loading and mass production and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 63
- 239000000446 fuel Substances 0.000 title claims abstract description 36
- 238000011068 loading method Methods 0.000 title claims abstract description 35
- 210000000170 cell membrane Anatomy 0.000 title claims abstract description 19
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- 239000012528 membrane Substances 0.000 claims abstract description 103
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- 239000010410 layer Substances 0.000 claims description 369
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- 238000000034 method Methods 0.000 claims description 50
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000009987 spinning Methods 0.000 claims description 22
- 239000006185 dispersion Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
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- 229920000642 polymer Polymers 0.000 claims description 13
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- 239000003795 chemical substances by application Substances 0.000 claims description 12
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
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- 238000007751 thermal spraying Methods 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000005520 cutting process Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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
Abstract
The application discloses a fuel cell membrane electrode with low platinum loading and mass production and a preparation method thereof, belonging to the technical field of fuel cells. The structure of the membrane electrode configuration is as follows: the anode gas diffusion layer, the anode microporous layer, the anode particle stacking type catalyst layer, the anode ionomer layer, the proton exchange membrane, the cathode fiber arrangement type catalyst layer, the cathode microporous layer and the cathode gas diffusion layer; the anode microporous layer comprises an anode drainage microporous layer and an anode water retention microporous layer. Wherein, the anode water-retaining microporous layer contains no platinum nano-particles, and the anode particle stacking catalyst layer contains platinum nano-particles; other components and structures are the same. According to the fuel cell membrane electrode structure, the anode adopts the particle stacked catalyst layer, the cathode adopts the fiber arrangement type catalyst layer, so that the preparation process difficulty is reduced, the utilization rate of noble metal platinum is improved, and the overall platinum consumption of the membrane electrode is reduced.
Description
Technical Field
The application belongs to the technical field of fuel cells, and particularly relates to a fuel cell membrane electrode with low platinum loading capacity and mass production and a preparation method thereof.
Background
Membrane electrodes are one of the most central and expensive parts of proton exchange membrane fuel cells. In the current mainstream technology, the membrane electrode is composed of a seven-layer structure including a Proton Exchange Membrane (PEM) located at the center, cathode and anode Catalyst Layers (CL) on both sides of the proton exchange membrane, a micro-porous layer (MPL) on the outer side of the catalyst layers, and a Gas Diffusion Layer (GDL) on the outer side. Because almost all chemical reactions in the fuel cell occur on the catalyst layer in the membrane electrode, the quality of the catalyst layer directly determines the quality of each key performance index of the fuel cell; and because almost all of the noble metal is supported on the catalyst layer, the cost of the catalyst layer may occupy a large portion of the total fuel cell cost.
The current catalyst layers can be classified into three categories according to the structure of the catalyst layers (see papers Liu Yong, ding Han, seldechun, etc.. Electro-spinning is used to prepare proton exchange membrane fuel cell catalyst layers for review [ J ]. Electrochemical, 2018,24 (6): 639.): the first type is a particle stacking type, which is the main stream type of commercial membrane electrode products at present, but the catalyst layer has low noble metal platinum utilization rate and is difficult to meet the large-scale commercial application requirement of fuel cell automobiles (taking prediction of the United states department of energy as an example, the mechanism considers that if the large-scale commercialization of the fuel cell automobiles is realized, the platinum dosage level of the proton exchange membrane fuel cell in 2020 should be lower than 0.125g/kW, and 2025 should be further reduced below 0.1g/kW, and the gap between the main stream technical level and the prediction is larger at present); the second type is columnar array type, for example, a nano film (nanostructured thin film, NSTF) catalyst layer prepared by 3M company in the united states is the first commercialized columnar array type catalyst layer, which can remarkably improve the utilization rate of noble metal platinum and reduce the platinum dosage in the catalyst layer, but has the common problems of high water management difficulty and easy water flooding phenomenon; the third type is fiber arrangement, which is mainly formed by arranging nanofibers or nanotubes prepared from catalyst slurry, wherein the nanofiber structure can improve the utilization rate of platinum, optimize the three-phase reaction interface of a catalyst layer and improve the proton conductivity, so that the catalyst layer is widely concerned, but the catalyst layer has the common problem that the mechanical strength is lower than that of a particle stacking type catalyst layer, and the catalyst layer is easy to damage in the process of assembling a membrane electrode; in addition, the fiber arrangement type catalyst layer has the common problem of being too sensitive to external humidification condition changes and having larger performance attenuation under low humidification working conditions. As shown in FIG. 1 (a), if two membrane electrodes with close power generation performance are provided, one of which is a particle stacked catalyst layer and one of which is a fiber arrangement type catalyst layer, when the relative humidity of the humidification of the cathode and anode is simultaneously reduced to 40%, the membrane electrode using the fiber arrangement type catalyst layer exhibits more remarkable performance degradation, as shown in FIG. 1 (b) (see paper: brodt M, han T, dale N, et al, in-situ performance, and durability of nanofiber fuel cell electrodes [ J ]. Journal of The Electrochemical Society,2014,162 (1): F84).
In addition, the current mainstream technology can be classified into two categories according to the substrate of the catalyst layer in the preparation process. The first is to prepare a catalyst layer on a microporous layer with the microporous layer as a substrate, so that a gas diffusion electrode (gas diffusion electrode, GDE) is formed by the diffusion layer, the microporous layer and the catalyst layer; the second type is to use a proton exchange membrane as a substrate, and prepare a catalyst layer on the proton exchange membrane, and this type of technology is called a catalyst coated membrane (catalyst coated membrane, CCM) technology.
In summary, for the three catalyst layer structures, the particle stacking type catalyst layer has the problems that the noble metal platinum utilization rate is low, the platinum consumption in the catalyst layer is large, and the large-scale commercialization requirement of the fuel cell automobile is difficult to meet; the columnar array type catalyst layer has the problems of large water management difficulty and easy water flooding; the fiber arrangement type catalyst layer has the common problems that the mechanical strength is lower than that of the particle stacking type catalyst layer, the membrane electrode is easy to damage in the process of assembling, and the mass production is difficult; in addition, the fiber arrangement type catalyst layer has the common problem of being too sensitive to external humidification condition changes and having larger performance attenuation under low humidification working conditions.
For the GDE technology and the CCM technology, compared with the GDE technology and the CCM technology, the GDE technology has the problem of larger proton conduction impedance; compared with the GDE technology, the CCM technology has the problem of larger multiphase mass transfer resistance of substances such as water, reaction gas and the like. In addition, if the CCM technology is used for both the cathode and anode of the membrane electrode, the problem of needing a catalyst layer which covers the cathode and anode uniformly, flatly and in alignment on both sides of a proton exchange membrane is also faced, and the process difficulty is increased. Especially when the mechanical strength of the catalyst layer is insufficient, if CCM technology is used for both the cathode and anode, the risk of damaging the catalyst layer during the manufacturing process is significantly increased.
In view of the foregoing problems in the prior art, it is desirable to provide a method for preparing a fuel cell membrane electrode that can achieve mass production, improve platinum utilization under low platinum loading, and overcome significant performance degradation under low humidification conditions.
Disclosure of Invention
In order to solve the problems, the application provides a novel configuration of a fuel cell membrane electrode aiming at the problems that the precious metal platinum utilization rate of a particle stacked catalyst layer is low, the platinum dosage in the catalyst layer is large, and the mechanical strength of a fiber arrangement type catalyst layer is lower than that of the particle stacked catalyst layer and the performance attenuation is large under the low humidification working condition.
The structure of the membrane electrode configuration is as follows: the anode gas diffusion layer, the anode microporous layer, the anode particle stacking type catalyst layer, the anode ionomer layer, the proton exchange membrane, the cathode fiber arrangement type catalyst layer, the cathode microporous layer and the cathode gas diffusion layer;
the anode microporous layer comprises an anode drainage microporous layer arranged near the anode gas diffusion layer and an anode water-retaining microporous layer arranged near the anode particle stacking type catalyst layer;
preparing an anode particle stacking type catalyst layer on the surface of the anode water-retaining microporous layer, and preparing a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane.
The method comprises the following steps: preparing an anode particle stacking type catalyst layer on the surface of the anode water-retaining microporous layer, and then preparing an anode ionomer layer on the anode particle stacking type catalyst layer; preparing a cathode fiber arrangement type catalyst layer on one side of the surface of the proton exchange membrane, connecting the other side with an anode ionomer layer, and integrally packaging the cathode microporous layer, the cathode gas diffusion layer and the membrane electrode structure according to the configuration sequence.
The anode water-retaining microporous layer contains no platinum nano particles, and the anode particle stacking catalyst layer contains platinum nano particles; the anode water-retaining microporous layer has the same composition and structure as the anode particle stacking type catalyst layer. The method aims to keep the microscopic morphologies of the anode catalyst layer and the anode water-retaining microporous layer as consistent as possible, and can effectively avoid flooding caused by pooling of liquid water at the interface between the anode catalyst layer and the anode water-retaining microporous layer.
Carbon loading in the anode drainage microporous layer is not less than 0.5mg/cm 2 And not higher than 2mg/cm 2 ；
The carbon loading in the anode water-retaining microporous layer is not less than 0.1mg/cm 2 And not higher than 1mg/cm 2 ；
Platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm 2 And not higher than 0.2mg/cm 2 ；
Platinum loading in the cathode fiber arrangement type catalyst layer is not less than 0.05mg/cm 2 And not higher than 0.5mg/cm 2 ；
The anode ionomer layer has a thickness of not less than 0.1 microns and not more than 2 microns.
Each of the anode particle stacked catalyst layer, the cathode fiber arranged catalyst layer and the cathode microporous layer has a uniform single-layer structure or a multi-layer structure of not more than 3 layers.
The preparation method of fuel cell membrane electrode with low platinum loading and mass production comprises four steps of anode preparation, cathode catalyst layer preparation, cathode microporous layer and gas diffusion layer preparation and membrane electrode assembly; the preparation of the anode, the preparation of the cathode catalyst layer, the preparation of the cathode microporous layer and the preparation of the gas diffusion layer can be carried out simultaneously, and finally the membrane electrode assembly part is carried out.
Further, the method comprises the steps of,
the preparation process of the anode comprises the following steps:
1) Respectively preparing anode drainage microporous layer slurry, anode water-retaining microporous layer slurry and anode catalyst layer slurry;
the raw materials of the anode drainage microporous layer slurry comprise carbon powder, hydrophobic high molecular polymer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retaining microporous layer slurry comprise porous carbon powder, perfluorosulfonic acid ionomer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the anode catalyst layer slurry comprises raw materials of Pt/C catalyst, deionized water, perfluorosulfonic acid ionomer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorosulfonic acid ionomer are solid or dispersion liquid;
the hydrophobic high molecular polymer comprises polytetrafluoroethylene or polyvinylidene fluoride;
the solvent comprises one or more of deionized water, ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the surfactant comprises polyvinylpyrrolidone;
the pore-forming agent comprises ammonium nitrate;
2) Sequentially preparing an anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacking type catalyst layer and an anode ionomer layer on an anode gas diffusion layer material;
the anode gas diffusion layer is a commercial anode gas diffusion layer product purchased directly or a self-made anode gas diffusion layer. In this part of the work, the anode gas diffusion layer is cut to a proper size and fixed in a proper orientation in a preparation apparatus of the anode drainage microporous layer.
Anode ionomer layer slurries include commercial perfluorosulfonic acid ionomer dispersion products, dilutions and concentrates of commercial perfluorosulfonic acid ionomer dispersion products, or self-configuring perfluorosulfonic acid ionomer dispersions.
The preparation process of the cathode catalyst layer comprises the following steps:
1) Preparing cathode catalyst slurry: uniformly mixing and dispersing the Pt/C catalyst, deionized water, perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the catalyst;
the perfluorosulfonic acid ionomer is a solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high polymer spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) Spinning by utilizing cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of a proton exchange membrane;
and cutting the proton exchange membrane to a proper size, spinning on one side of the proton exchange membrane, which is not covered by the protective shell, and covering the protective shell with stronger mechanical strength on the other side, wherein the protective shell is fixed at a proper position in a preparation device of the cathode catalyst layer in a proper orientation.
The cathode microporous layer and the cathode gas diffusion layer are of a commercial cathode microporous layer and gas diffusion layer integrated composite structure or the cathode microporous layer is prepared on the surface of the cathode gas diffusion layer by itself.
The membrane electrode assembly process comprises the following steps: before packaging, the protective shell originally covered on the proton exchange membrane is completely removed, the layers are aligned according to the membrane electrode configuration, and sealing frames are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer, and then the membrane electrode is packaged in a hot-pressing mode.
Preferably, the method for preparing each layer of the anode comprises spraying or coating, in particular comprises using an ultrasonic thermal spraying device or a slit coating device.
The spinning device comprises an electrostatic spinning device or an air spinning device.
The platinum loading or carbon loading in each layer is verified through detection, and the detection method comprises a weighing method, an X-ray fluorescence spectrometry method and a thermogravimetric analysis method.
The application has the beneficial effects that:
1. the anode adopts the particle stacked catalyst layer and the cathode adopts the fiber arrangement catalyst layer in the fuel cell membrane electrode structure, thereby greatly improving the utilization rate of noble metal platinum (the electrochemical active area of the cathode catalyst layer is up to 74.19 m) while reducing the preparation process difficulty 2 /g pt The platinum consumption of the cathode is lower than 0.075 g/kW), and the platinum consumption of the whole membrane electrode is reduced(the overall platinum usage of the membrane electrode is less than 0.125 g/kW).
2. In the configuration of the fuel cell membrane electrode, a particle stacking type catalyst layer is prepared on the surface of a water-retaining microporous layer at the anode side, and a fiber arrangement type catalyst layer is prepared on the surface of a proton exchange membrane at the cathode side; the cathode catalyst layer and the anode catalyst layer can be prepared respectively, the step of turning over the proton exchange membrane is avoided in the preparation process, and the flow line production and batch preparation are facilitated.
3. In the process of preparing the cathode fiber arrangement type catalyst layer, the protective shell with stronger mechanical property can be reserved on the other side of the proton exchange membrane, so that the mechanical strength of the catalyst layer substrate is ensured, and the risk of damaging the fiber arrangement type catalyst layer in the preparation process is effectively reduced.
4. The water-retaining microporous layer is arranged on the anode, so that the performance attenuation of the membrane electrode under the low humidification working condition is remarkably relieved.
Drawings
FIGS. 1 (a) and 1 (b) are a comparison of the performance of a particle-stacked catalyst layer versus a fiber-aligned catalyst layer under different humidification conditions;
FIG. 2 is a schematic illustration of a membrane electrode configuration;
FIG. 3 is a schematic diagram of the overall process flow for batch preparation of membrane electrodes;
FIG. 4 is a schematic illustration of an anode preparation process flow;
FIG. 5 is a schematic illustration of a process flow for preparing a cathode catalyst layer;
FIG. 6 is a scanning electron micrograph of the surface of an anode drainage microporous layer;
FIG. 7 is a scanning electron micrograph of the surface of an anode water-retaining microporous layer;
FIG. 8 is a scanning electron micrograph of the surface of an anode pellet stacked catalyst layer;
FIG. 9 is a scanning electron micrograph of the surface of a cathode fiber arranged catalyst layer;
FIG. 10 is a graph showing the results of a polarization curve test of a membrane electrode;
FIG. 11 is a cyclic voltammetry test result for a membrane electrode;
FIG. 12 is a graph showing a comparison of the power generation performance of membrane electrodes under different humidification conditions.
Detailed Description
The application is described in further detail below with reference to the attached drawings and specific examples:
the present application will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present application more apparent. 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.
The application provides a new configuration of a fuel cell membrane electrode, aiming at the problems that the utilization rate of noble metal platinum in a particle stacking type catalyst layer is low and the dosage of platinum in the catalyst layer is large, and the mechanical strength of a fiber arrangement type catalyst layer is lower than that of the particle stacking type catalyst layer and the performance attenuation is large under the low humidification working condition.
As shown in fig. 2, the membrane electrode structure of the fuel cell with low platinum loading and mass production is as follows: the anode gas diffusion layer, the anode microporous layer, the anode particle stacking type catalyst layer, the anode ionomer layer, the proton exchange membrane, the cathode fiber arrangement type catalyst layer, the cathode microporous layer and the cathode gas diffusion layer;
it is noted that the anode microporous layer includes an anode drainage microporous layer disposed in the near-anode gas diffusion layer, and an anode water retention microporous layer disposed in the near-anode particle stacked catalyst layer; the material composition and the preparation process of the anode water-retaining microporous layer are consistent with those of the anode particle stacking type catalyst layer, and the anode water-retaining microporous layer comprises preparation equipment, key parameters (such as temperature and the like) of the preparation process, key parameters of slurry formula (such as the selection of a solvent, the mass ratio of porous carbon to perfluorosulfonic acid ionomer, the total solid mass content of the slurry and the like); the difference is only that platinum nanoparticles are supported on the porous carbon in the anode catalyst layer, whereas platinum nanoparticles are not supported on the porous carbon in the anode water-retaining microporous layer. The method aims to keep the microscopic morphologies of the anode catalyst layer and the anode water-retaining microporous layer as consistent as possible, and can effectively avoid flooding caused by pooling of liquid water at the interface between the anode catalyst layer and the anode water-retaining microporous layer. This arrangement of the anode water-retaining microporous layer is original.
Preparing an anode particle stacking type catalyst layer on the surface of the anode water-retaining microporous layer, and then preparing an anode ionomer layer on the anode particle stacking type catalyst layer;
preparing a cathode fiber arrangement type catalyst layer on one side of the surface of the proton exchange membrane, connecting the other side with an anode ionomer layer, and integrally packaging the cathode microporous layer, the cathode gas diffusion layer and the membrane electrode structure according to the configuration sequence.
Each of the anode particle stacked catalyst layer, the cathode fiber arranged catalyst layer and the cathode microporous layer has a uniform single-layer structure or a multi-layer structure of not more than 3 layers.
Therefore, the application also provides a batch preparation process flow for the membrane electrode with the configuration, as shown in fig. 3. The technological process is divided into four parts, namely anode preparation, cathode catalyst layer preparation, cathode microporous layer and gas diffusion layer preparation and membrane electrode assembly. The preparation of the anode, the preparation of the cathode catalyst layer, the preparation of the cathode microporous layer and the preparation of the gas diffusion layer are not sequential, and can be performed in parallel, and the membrane electrode assembly part is performed after the steps are completed.
Anode preparation
The anode preparation process flow is shown in fig. 4. The preparation of the anode gas diffusion layer and the preparation of the anode slurry can be performed in parallel without sequence, and the preparation of the anode drainage microporous layer can be performed after the two processes are completed.
1) Respectively preparing anode drainage microporous layer slurry, anode water-retaining microporous layer slurry and anode catalyst layer slurry;
the preparation process of each slurry comprises the steps of firstly weighing each raw material according to the required proportion, then respectively mixing the raw materials of each slurry, and uniformly dispersing to obtain the preparation of each slurry.
The raw materials of the anode drainage microporous layer slurry comprise carbon powder, hydrophobic high molecular polymer and solvent; the porous ceramic material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retaining microporous layer slurry comprise porous carbon powder, perfluorosulfonic acid ionomer and solvent; the porous ceramic material also comprises a surfactant and a pore-forming agent;
the anode catalyst layer slurry comprises raw materials of Pt/C catalyst, deionized water, perfluorosulfonic acid ionomer and solvent; the porous ceramic material also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorosulfonic acid ionomer are solid or dispersion liquid;
the hydrophobic high molecular polymer comprises polytetrafluoroethylene or polyvinylidene fluoride;
the solvent comprises one or more of deionized water, ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the surfactant comprises polyvinylpyrrolidone;
the pore-forming agent comprises ammonium nitrate;
2) Sequentially preparing a covered anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacking type catalyst layer and an anode ionomer layer on an anode gas diffusion layer material;
the anode gas diffusion layer is a commercial anode gas diffusion layer product purchased directly or a self-made anode gas diffusion layer. In this part of the work, the anode gas diffusion layer is cut to a proper size and fixed in a proper orientation in a preparation apparatus of the anode drainage microporous layer.
Methods of preparing the layers include spraying or coating, including specifically using an ultrasonic thermal spraying apparatus or a slot die apparatus.
The platinum loading or carbon loading in each layer is verified through detection, and the detection method comprises a weighing method, an X-ray fluorescence spectrometry method and a thermogravimetric analysis method.
The design value of carbon load in the anode drainage microporous layer is not lower than 0.5mg/cm 2 And not higher than 2mg/cm 2 。
The design value of carbon load in the anode water-retaining microporous layer is not less than 0.1mg/cm 2 And not higher than 1mg/cm 2 。
The design value of platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm 2 And not higher than 0.2mg/cm 2 。
The anode ionomer layer has a thickness of not less than 0.1 μm and not more than 2 μm.
In the preparation process of the anode particle stacking type catalyst layer, a preparation device consistent with the anode water-retaining microporous layer is adopted to prepare the anode particle stacking type catalyst layer on the surface of the anode water-retaining microporous layer.
Anode ionomer layer slurries include commercial perfluorosulfonic acid ionomer dispersion products (e.g., nafion D520, nafion D2020, etc. from dupont, usa), dilutions or concentrates of commercial perfluorosulfonic acid ionomer dispersion products, or self-configuring perfluorosulfonic acid ionomer dispersions.
Cathode catalyst layer preparation
The process flow for preparing the cathode catalyst layer is shown in fig. 5. The preparation of the proton exchange membrane and the preparation of the cathode catalyst slurry can be performed in parallel without sequence, and the preparation of the cathode fiber arranged catalyst layer can be performed after the two processes are completed.
1) Preparing cathode catalyst slurry: uniformly mixing and dispersing the Pt/C catalyst, deionized water, perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the catalyst;
the perfluorosulfonic acid ionomer is a solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high polymer spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) Spinning by utilizing cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of a proton exchange membrane;
cutting the proton exchange membrane to a proper size, spinning on one side of the proton exchange membrane, which is not covered by the protective shell, and fixing the protective shell with stronger mechanical strength on the spinning device in a proper direction on the other side of the proton exchange membrane; and is fixed in place in the preparation device of the cathode catalyst layer.
The spinning device comprises an electrostatic spinning device or an air spinning device;
the design value of platinum carrying capacity in the cathode fiber arrangement type catalyst layer is not lower than 0.05mg/cm 2 And not higher than 0.5mg/cm 2 ；
The platinum loading in the cathode fiber arranged catalyst layer is verified through detection, and the detection method comprises a weighing method, an X-ray fluorescence spectrometry method and a thermogravimetric analysis method.
Cathode microporous layer and gas diffusion layer preparation
The cathode microporous layer and the cathode gas diffusion layer are of a commercial cathode microporous layer and gas diffusion layer integrated composite structure or the cathode microporous layer is prepared on the surface of the cathode gas diffusion layer by itself.
The cathode micropore layer is of a single-layer structure or a multi-layer composite structure with no more than 3 layers and is made of uniform materials. In addition, in this part of the work, the cathode microporous layer and the cathode gas diffusion layer are cut to a proper size.
Membrane electrode assembly
In the membrane electrode assembly process, according to the membrane electrode configuration shown in fig. 2, each layer structure is ensured to be sequentially arranged as shown in fig. 2, namely an anode gas diffusion layer, an anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacking type catalyst layer, an anode ionomer layer, a proton exchange membrane, a cathode fiber arrangement type catalyst layer, a cathode microporous layer and a cathode gas diffusion layer, and each layer structure is aligned. And carrying out hot-pressing packaging on each prepared composite structure. Before packaging, the protective shell originally covered on the proton exchange membrane is completely removed, and sealing frames with proper shapes and thickness are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer. After the steps are finished, the membrane electrode is packaged in a hot-pressing mode by using proper pressure and temperature, and the membrane electrode assembly work is finished.
Example 1
The application provides a fuel cell membrane electrode with low platinum loading and mass production and a preparation method thereof. The configuration of the membrane electrode is shown in fig. 2, in this example, the anode gas diffusion layer is made of TGP-H-060 type conductive carbon paper of Toray, japan, and the water-retaining microporous layer near the gas diffusion layer is more hydrophobic and the water-retaining microporous layer near the anode catalyst layer is relatively less hydrophobic. The cathode is directly a commercial product with integrated gas diffusion layer and microporous layer, and the model is H23-cx653 of Germany Cordybao company (Freudenberg).
Anode preparation
The anode preparation process flow is shown in fig. 4. The preparation of the anode gas diffusion layer and the preparation of the anode slurry can be performed in parallel without sequence, and the preparation of the anode drainage microporous layer can be performed after the two processes are completed.
1) Respectively preparing anode drainage microporous layer slurry, anode water-retaining microporous layer slurry and anode catalyst layer slurry;
the process of preparing each slurry is that firstly, each raw material is weighed according to the required proportion, then, the raw materials of each slurry are respectively mixed, firstly, ultrasonic dispersion is carried out for 0.5 hour, then high-speed shearing dispersion is carried out for 1 hour, and finally, ultrasonic dispersion is carried out for 0.5 hour for the second time;
the anode drainage microporous layer slurry is prepared from Vulcan XC-72 type conductive carbon powder of Kabot Company (CABOT), polytetrafluoroethylene powder and isopropanol solvent, wherein the mass ratio of the carbon powder to the polytetrafluoroethylene powder is 4:1, and the total solid mass content in the anode drainage microporous layer slurry is 2.5%.
The anode water-retaining microporous layer slurry is prepared from Ketjen black ECP-600JD conductive carbon powder of Japanese LION corporation (LION), nafion D520 type perfluorosulfonic acid ionomer dispersion of Dupont corporation (Dupont) of U.S., deionized water and isopropanol solvent, wherein the mass ratio of carbon powder to perfluorosulfonic acid ionomer is 1:0.7, the mass ratio of water to isopropanol is 1:5, and the total solid mass content in the anode water-retaining microporous layer slurry is 2.5%.
The anode catalyst layer slurry is prepared from Pt/C catalyst (wherein the mass content of Pt is 40%, and the carbon carrier is Ketjenback ECP-600JD conductive carbon powder), deionized water, nafion D520 type perfluorosulfonic acid ionomer dispersion liquid of Dupont, U.S. and isopropanol solvent; wherein the mass ratio of the carbon carrier in the Pt/C catalyst to the perfluorosulfonic acid ionomer in the anode catalyst layer slurry is 1:0.7, the mass ratio of water to isopropanol is 1:5, and the total solid mass content in the anode catalyst layer slurry is 2.5%.
2) The commercial anode gas diffusion layer product purchased directly was cut to the appropriate dimensions and fixed in the appropriate orientation in the anode drainage microporous layer making apparatus, and the covered anode drainage microporous layer, anode water retention microporous layer, anode particulate stacked catalyst layer, and anode ionomer layer were prepared sequentially using an ultrasonic thermal spray process. The ultrasonic thermal spraying equipment adopts PRISM-400BT type products of USI company in the United states, and the spraying temperature is 100 ℃.
The spray coating slurry for the anode ionomer layer was directly a nafion d520 perfluorosulfonic acid ionomer dispersion from Dupont, usa, having an average thickness of 0.3 microns after preparation.
The platinum or carbon loading in each layer was verified by weighing, X-ray fluorescence spectroscopy, or thermogravimetric analysis.
Wherein the total carbon content of the anode drainage microporous layer after the preparation is 1.2mg/cm 2 The typical surface topography is shown in fig. 6.
The total carbon content of the anode water-retaining microporous layer after the preparation is 0.25mg/cm 2 The typical surface topography is shown in fig. 7.
The total platinum content of the anode particle stacking type catalyst layer after the preparation was 0.05mg/cm 2 The typical surface topography is shown in fig. 8.
The preparation scheme ensures that the microscopic morphology of the anode particle stacked catalyst layer is basically consistent with that of the anode water-retaining microporous layer, and can effectively avoid flooding caused by liquid water pooling at the interface between the anode catalyst layer and the anode water-retaining microporous layer.
Cathode catalyst layer preparation
The process flow for preparing the cathode catalyst layer is shown in fig. 5. The preparation of the proton exchange membrane and the preparation of the cathode catalyst slurry can be performed in parallel without sequence, and the preparation of the cathode fiber arranged catalyst layer can be performed after the two processes are completed.
1) Preparing cathode catalyst slurry: raw materials of the cathode catalyst slurry comprise Pt/C catalyst (Pt mass content is 40%), deionized water, isopropanol organic solvent, polyacrylic acid (average molecular weight is 45 ten thousand) and Nafion D520 type perfluorosulfonic acid ionomer dispersion liquid of Dupont company (Dupont) in U.S.A.; wherein the mass ratio of Pt/C catalyst to perfluorosulfonic acid ionomer is 2.5:1, the mass ratio of water to isopropanol is 1:3, the mass ratio of polyacrylic acid to perfluorosulfonic acid ionomer is 1:1, and the total solid mass content in the cathode catalyst slurry is 7.5%. The dispersion method of the spinning slurry of the cathode fiber arranged catalyst layer is to stir for 12 hours by using a magnet first and then to disperse for 1 hour by shearing at high speed.
2) Spinning by utilizing cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of a proton exchange membrane;
the cathode fiber arranged catalyst layer is prepared by adopting an electrostatic spinning method, and electrostatic spinning equipment adopts Elite series products of Beijing Yongkangle science and technology development Co., ltd, wherein the spinning temperature is set to 35 ℃, the humidity is set to RH15%, the positive high voltage is set to 6kV, and the negative high voltage is set to-3 kV.
The proton exchange membrane was prepared by Gore, america, gore, having a thickness of 15 μmMembrane series products. After the proton exchange membrane is cut to a proper size, the proton exchange membrane is fixed on a roller wire collector of electrostatic spinning equipment, the surface covered with a protective shell faces to a roller, the nano fibers are directly collected by adopting a roller wire collecting method, the rotating speed of the roller is 120 revolutions per minute, and the distance between a spinning needle head and the roller is 15cm.
The platinum loading in the cathode fiber arranged catalyst layer is detected and verified by a weighing method, an X-ray fluorescence spectrometry method or a thermogravimetric analysis method, and the total platinum content after the preparation of the cathode fiber arranged catalyst layer is 0.075mg/cm 2 The typical surface topography is shown in fig. 9.
Cathode microporous layer and gas diffusion layer preparation
The cathode microporous layer and the cathode gas diffusion layer adopt a commercial cathode microporous layer and gas diffusion layer integrated composite structure, and the model is H23-cx653 of Germany Kedberg company (Freudenberg). In this part of the work, the cathode microporous layer and the cathode gas diffusion layer also need to be cut to a proper size.
Membrane electrode assembly
In the membrane electrode assembly process, the protective shell originally covered on the proton exchange membrane is completely removed, sealing gaskets with proper shapes and thickness of 135 micrometers are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer, and then the hot pressing pressure is set to be 1 ton, the temperature is 120 ℃, and the pressure maintaining time is set to be 30 seconds. According to the membrane electrode configuration shown in fig. 2, each layer structure is ensured to be sequentially arranged as shown in fig. 2, namely an anode gas diffusion layer, an anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacking type catalyst layer, an anode ionomer layer, a proton exchange membrane, a cathode fiber arrangement type catalyst layer, a cathode microporous layer and a cathode gas diffusion layer, and all the layer structures are aligned for hot-press packaging.
The low platinum loading fuel cell membrane electrode prepared according to the process described in this example shows better performance and higher noble metal platinum utilization. Fig. 10 shows the polarization curve test results of the membrane electrode under the hydrogen/air test condition when the hydrogen metering ratio is 1.5 and the air metering ratio is 2.5. As shown in the figure, under the test conditions, the peak power of the membrane electrode exceeds 1000mW/cm 2 The total platinum consumption of the cathode and anode electrodes of the membrane electrode is lower than 0.125g/kW, wherein the cathode platinum consumption is lower than 0.075g/kW.
Figure 11 shows the cyclic voltammetry test results for this membrane electrode. As shown in the figure, the electrochemical active area of the membrane electrode cathode fiber arrangement type catalyst layer is 74.19m at 25 DEG C 2 /g pt The higher noble metal platinum utilization rate of the cathode is the main reason for the lower total platinum consumption of the membrane electrode.
Due to the arrangement of the anode water-retaining microporous layer, the performance attenuation of the membrane electrode under the low humidification condition is effectively controlled, as shown in fig. 12, if the anode humidification relative humidity is kept to be 100%, even if the cathode humidification relative humidity is reduced from 100% to 0%, the performance of the membrane electrode is not obviously reduced; continuing to maintain the cathode humidification relative humidity at 0%, decreasing the anode humidification relative humidity from 100% to 30%, the performance degradation of the membrane electrode still being within acceptable limits; when the relative humidity of the cathode and anode is reduced to 0%, the stability of the membrane electrode test is reduced, and a serious membrane drying phenomenon occurs in a low current density area, the performance is seriously reduced, but partial recovery is realized in a high current density area. All the above phenomena strongly prove the function of the anode water-retaining microporous layer.
Claims (10)
1. The membrane electrode of the fuel cell with low platinum loading and mass production is characterized in that the structure of the membrane electrode configuration is as follows: the anode gas diffusion layer, the anode microporous layer, the anode particle stacking type catalyst layer, the anode ionomer layer, the proton exchange membrane, the cathode fiber arrangement type catalyst layer, the cathode microporous layer and the cathode gas diffusion layer;
the anode microporous layer comprises an anode drainage microporous layer arranged near the anode gas diffusion layer and an anode water-retaining microporous layer arranged near the anode particle stacking type catalyst layer;
the raw materials of the anode drainage microporous layer comprise carbon powder, hydrophobic high molecular polymer and solvent; the raw materials of the anode water-retaining microporous layer comprise porous carbon powder, perfluorosulfonic acid ionomer and solvent;
preparing an anode particle stacking type catalyst layer on the surface of the anode water-retaining microporous layer, and preparing a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane.
2. A low platinum loading, mass produced fuel cell membrane electrode according to claim 1,
the anode water-retaining microporous layer contains no platinum nano particles, and the anode particle stacking catalyst layer contains platinum nano particles; the anode water-retaining microporous layer has the same composition and structure as the anode particle stacking type catalyst layer.
3. A low platinum loading, mass produced fuel cell membrane electrode according to claim 1,
carbon loading in the anode drainage microporous layer is not less than 0.5mg/cm 2 And not higher than 2mg/cm 2 ；
The carbon loading in the anode water-retaining microporous layer is not less than 0.1mg/cm 2 And not higher than 1mg/cm 2 ；
Platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm 2 And not higher than 0.2mg/cm 2 ；
Platinum loading in the cathode fiber arrangement type catalyst layer is not less than 0.05mg/cm 2 And not higher than 0.5mg/cm 2 ；
The anode ionomer layer has a thickness of not less than 0.1 microns and not more than 2 microns.
4. The low platinum loading, mass produced fuel cell membrane electrode according to claim 1 wherein each of said anode particle stacked catalyst layer, cathode fiber arranged catalyst layer and cathode microporous layer has a uniform single layer structure or a multilayer structure of no more than 3 layers.
5. A method for preparing a low platinum loading mass produced fuel cell membrane electrode according to claim 1,
the method comprises four parts, namely anode preparation, cathode catalyst layer preparation, cathode microporous layer and gas diffusion layer preparation and membrane electrode assembly; the preparation of the anode, the preparation of the cathode catalyst layer, the preparation of the cathode microporous layer and the preparation of the gas diffusion layer can be carried out simultaneously, and finally the membrane electrode assembly part is carried out.
6. The method for preparing a membrane electrode assembly for a mass-produced fuel cell with a low platinum loading according to claim 5,
the preparation process of the anode comprises the following steps:
1) Respectively preparing anode drainage microporous layer slurry, anode water-retaining microporous layer slurry and anode catalyst layer slurry;
the raw materials of the anode drainage microporous layer slurry comprise carbon powder, hydrophobic high molecular polymer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retaining microporous layer slurry comprise porous carbon powder, perfluorosulfonic acid ionomer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the anode catalyst layer slurry comprises raw materials of Pt/C catalyst, deionized water, perfluorosulfonic acid ionomer and solvent; further, the porous ceramic material also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorosulfonic acid ionomer are solid or dispersion liquid;
the hydrophobic high molecular polymer comprises polytetrafluoroethylene or polyvinylidene fluoride;
the solvent comprises one or more of deionized water, ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the surfactant comprises polyvinylpyrrolidone;
the pore-forming agent comprises ammonium nitrate;
2) Sequentially preparing an anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacking type catalyst layer and an anode ionomer layer on an anode gas diffusion layer material; the anode ionomer layer slurry is a perfluorosulfonic acid ionomer dispersion.
7. The method for preparing a membrane electrode assembly for a mass-produced fuel cell with a low platinum loading according to claim 5,
the preparation process of the cathode catalyst layer comprises the following steps:
1) Preparing cathode catalyst slurry: uniformly mixing and dispersing the Pt/C catalyst, deionized water, perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the catalyst;
the perfluorosulfonic acid ionomer is a solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high polymer spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) Spinning by using cathode catalyst slurry, and preparing a cathode fiber arranged catalyst layer on the surface of the proton exchange membrane.
8. The method for preparing a membrane electrode for a fuel cell with low platinum loading and mass production according to claim 5, wherein the membrane electrode assembly process comprises the following steps: before packaging, the protective shell originally covered on the proton exchange membrane is completely removed, the layers are aligned according to the membrane electrode configuration, and sealing frames are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer, and then the membrane electrode is packaged in a hot-pressing mode.
9. The method of preparing a low platinum loading, mass produced fuel cell membrane electrode according to claim 6 wherein said method of preparing each layer comprises spraying or coating, in particular by using an ultrasonic thermal spraying device or a slot die coating device.
10. The method for preparing a low platinum loading mass produced fuel cell membrane electrode according to claim 7 wherein said spinning means comprises an electrospinning means or an air spinning means.
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