CN114447347A - Fuel cell membrane electrode with low platinum loading capacity and mass production and preparation method thereof - Google Patents
Fuel cell membrane electrode with low platinum loading capacity and mass production and preparation method thereof Download PDFInfo
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- 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 invention discloses a fuel cell membrane electrode with low platinum loading capacity 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 in sequence: an anode gas diffusion layer, an anode 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; the anode microporous layer comprises an anode drainage microporous layer and an anode water retention microporous layer. The anode water-retention microporous layer does not contain platinum nanoparticles, and the anode particle stacked catalyst layer contains platinum nanoparticles; other components and structures are the same. According to the fuel cell membrane electrode structure, the anode adopts the particle stacked catalyst layer, and the cathode adopts the fiber arrangement catalyst layer, so that the difficulty of the preparation process is reduced, the utilization rate of noble metal platinum is improved, and the platinum dosage of the whole membrane electrode is reduced.
Description
Technical Field
The invention 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 components of pem fuel cells. In the currently mainstream technology, the membrane electrode is composed of a seven-layer structure including a Proton Exchange Membrane (PEM) located at the center, a cathode Catalyst Layer (CL) and an anode Catalyst Layer (CL) located at both sides of the PEM, a micro-porous layer (MPL) located at the outer side of the catalyst layer, and a Gas Diffusion Layer (GDL) located at the outermost 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 since almost all of the noble metal is supported on the catalyst layer, the cost of the catalyst layer will account for a large portion of the overall fuel cell cost.
The current catalyst layers can be classified into three categories according to the structure of the catalyst layers (see papers: liu courage, ding culvert, sedun, etc.. the preparation of proton exchange membrane fuel cell catalyst layers by electrostatic spinning is reviewed [ J ] electrochemistry, 2018,24(6): 639.): the first type is a particle stacking type, which is the mainstream type of the current commercialized membrane electrode product, but the catalyst layer generally has the problems that the utilization rate of noble metal platinum is low, and the requirement of large-scale commercialized application of a fuel cell automobile is difficult to meet (taking prediction of the U.S. department of energy as an example, the organization considers that if large-scale commercialization of the fuel cell automobile is realized, the platinum dosage level of a proton exchange membrane fuel cell in 2020 should be lower than 0.125g/kW, the platinum dosage level of the proton exchange membrane fuel cell in 2025 should be further reduced to be lower than 0.1g/kW, and the difference between the current mainstream technical level and the prediction is large); the second type is a columnar array type, for example, a nano-thin film (NSTF) catalyst layer prepared by 3M company in the united states is a first commercialized columnar array type catalyst layer, which can significantly improve the utilization rate of noble metal platinum and reduce the platinum dosage in the catalyst layer, but generally has the problems of high water management difficulty and easy occurrence of a water flooding phenomenon; the third type is a fiber arrangement type, which is mainly formed by arranging nano fibers or nano tubes prepared from catalyst slurry, wherein the nano fiber 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 generally has the problems that the mechanical strength is lower than that of a particle stacked catalyst layer and the catalyst layer is easy to damage in the membrane electrode assembling process; in addition, the fiber arrangement type catalyst layer also generally has the problems of being too sensitive to the change of external humidification conditions and having larger performance attenuation under the working condition of low humidification. As shown in FIG. 1(a), if there are two membrane electrodes with close power generation performance when The relative humidity of The cathode and anode is 100%, one of them uses a particle-stacked catalyst layer and The other uses a fiber-arranged catalyst layer, The membrane electrode using The fiber-arranged catalyst layer shows more obvious performance degradation when The relative humidity of The cathode and anode is reduced to 40% at The same time, as shown in FIG. 1(b) (see The paper: Brodt M, Han T, Dale N, et al. simulation, in-situ performance, and dual of nano-functional cell electrodes [ J ]. Journal of The Electrochemical source, 2014,162(1): F84.).
Further, the current mainstream technologies can be classified into two categories, classified according to the substrate of the catalyst layer in the production process. The first type is that a microporous layer is taken as a substrate, a catalyst layer is prepared on the microporous layer, and a Gas Diffusion Electrode (GDE) is formed by a diffusion layer, the microporous layer and the catalyst layer; the second type is a technique of preparing a catalyst layer on a proton exchange membrane (pem) using the pem as a substrate, and is called a Catalyst Coated Membrane (CCM) technique.
In conclusion, aiming at the three catalyst layer structures, the problems that the utilization rate of noble metal platinum is low, the platinum dosage in the catalyst layer is large, and the large-scale commercialization requirement of a fuel cell automobile is difficult to meet commonly exist in the particle stacking type catalyst layer; the columnar array type catalyst layer generally has the problems of high water management difficulty and easy occurrence of flooding phenomenon; the fiber arrangement type catalyst layer generally has the problems that the mechanical strength is lower than that of the particle stacking type catalyst layer, and the membrane electrode is easy to damage and difficult to produce in batches in the process of assembling the membrane electrode; in addition, the fiber arrangement type catalyst layer also generally has the problems of being too sensitive to the change of external humidification conditions and having larger performance attenuation under the working condition of low humidification.
Aiming at the problems that the GDE technology and the CCM technology have larger proton conduction impedance compared with the CCM technology; 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 the anode of the membrane electrode, the problem that catalyst layers covering the cathode and the anode need to be uniformly, flatly and aligned on both sides of a proton exchange membrane film is also faced, and the process difficulty is increased. Especially when the mechanical strength of the catalyst layer is insufficient, if CCM technology is applied to both cathode and anode electrodes, the risk of damage to the catalyst layer during the production process is significantly increased.
In view of the above problems in the prior art, it is desirable to provide a method for preparing a fuel cell membrane electrode, which can realize mass production, improve the utilization rate of platinum under the condition of low platinum loading capacity, and overcome the great performance degradation under the low humidification condition.
Disclosure of Invention
In order to solve the problems, the invention provides a novel structure of a membrane electrode of a fuel cell aiming at the problems that the utilization rate of noble metal platinum of a particle stacking type 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 stacking type catalyst layer, and the performance attenuation is large under the low-humidification working condition.
The structure of the membrane electrode configuration is as follows in sequence: an anode gas diffusion layer, an anode 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;
the anode microporous layer comprises an anode drainage microporous layer arranged close to the anode gas diffusion layer and an anode water retention microporous layer arranged close to the anode particle stacking type catalyst layer;
preparing an anode particle stacked catalyst layer on the surface of the anode water-retention microporous layer, and preparing a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane.
The method specifically comprises the following steps: preparing an anode particle stacking type catalyst layer on the surface of the anode water-retention 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 of the surface of the proton exchange membrane with an anode ionomer layer, and integrally packaging the cathode microporous layer, the cathode gas diffusion layer and the membrane electrode according to the configuration sequence.
The components of the anode water-retention microporous layer do not contain platinum nanoparticles, and the components of the anode particle stacked catalyst layer contain platinum nanoparticles; the anode water-retention microporous layer and the anode particle stacked catalyst layer have the same other components and structures. The aim is to keep the microcosmic appearances of the anode catalyst layer and the anode water-retaining microporous layer consistent as much as possible, and effectively avoid the flooding caused by the pooling of liquid water at the interface between the anode catalyst layer and the anode water-retaining microporous layer.
The carbon loading in the anode drainage microporous layer is not less than 0.5mg/cm2And not higher than 2mg/cm2；
The carbon loading capacity in the anode water-retention microporous layer is not less than 0.1mg/cm2And not higher than 1mg/cm2；
The platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm2And not higher than 0.2mg/cm2；
The platinum loading capacity in the cathode fiber arrangement type catalyst layer is not less than 0.05mg/cm2And not higher than 0.5mg/cm2；
The thickness of the anodic ionomer layer is not less than 0.1 microns and not more than 2 microns.
Each layer structure of the anode particle stacking type catalyst layer, the cathode fiber arrangement type catalyst layer and the cathode microporous layer is a uniform single-layer structure or a multi-layer structure of not more than 3 layers.
A preparation method of fuel cell membrane electrode with low platinum loading and mass production comprises four parts, namely anode preparation, cathode catalyst layer preparation, preparation of cathode microporous layer and gas diffusion layer, 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 gas diffusion layer can be simultaneously carried out, and finally the membrane electrode assembly part is carried out.
Further, the air conditioner is provided with a fan,
the preparation process of the anode comprises the following steps:
1) respectively preparing anode drainage microporous layer slurry, anode water retention 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 material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retention microporous layer slurry comprise porous carbon powder, perfluorinated sulfonic acid ionomer and a solvent; further, the material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode catalyst layer slurry comprise a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer and a solvent; further, the material also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorinated sulfonic 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) on the anode gas diffusion layer material, preparing an anode drainage microporous layer, an anode water-retention microporous layer, an anode particle stacked catalyst layer and an anode ionomer layer in turn;
the anode gas diffusion layer is a commercially available anode gas diffusion layer product directly purchased or a self-made anode gas diffusion layer. In this part of the work, the anode gas diffusion layer is cut to size and fixed in place in the anode drain microporous layer manufacturing apparatus in the proper orientation.
The anode ionomer layer slurry includes a commercial perfluorosulfonic acid ionomer dispersion product, a dilution and concentrate of a commercial perfluorosulfonic acid ionomer dispersion product, or a self-formulated perfluorosulfonic acid ionomer dispersion.
The preparation process of the cathode catalyst layer comprises the following steps:
1) preparing cathode catalyst slurry: uniformly mixing and dispersing a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the composite material;
the perfluorosulfonic acid ionomer is solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high molecular spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) spinning by using the cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of the 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 simultaneously covering the protective shell with stronger mechanical strength on the other side of the proton exchange membrane to be fixed at a proper position in the 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.
The membrane electrode assembly process comprises the following steps: the protective shell originally covered on the proton exchange membrane is completely uncovered before packaging, all layers are aligned according to the configuration of the membrane electrode, and the membrane electrode is subjected to hot-press packaging after sealing frames are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer.
Preferably, the method for preparing the anode layers comprises spraying or coating, and particularly comprises utilizing an ultrasonic thermal spraying device or a slot coating device.
The spinning device comprises an electrostatic spinning device or a gas spinning device.
And verifying the platinum loading or the carbon loading in each layer by detection, wherein the detection method comprises a weighing method, an X-ray fluorescence spectrometry and a thermogravimetric analysis.
The invention has the beneficial effects that:
1. the anode in the membrane electrode structure of the fuel cell adopts the particle stacked catalyst layer, and the cathode adopts the fiber arrangement catalyst layer, so that the difficulty of the preparation process is reduced, and the utilization rate of noble metal platinum can be greatly improved (the electrochemical active area of the cathode catalyst layer is as high as 74.19 m)2/gptThe platinum dosage of the cathode is lower than 0.075g/kW), and the platinum dosage of the whole membrane electrode is reduced (the platinum dosage of the whole membrane electrode is lower than 0.125 g/kW).
2. According to the configuration of the fuel cell membrane electrode, the particle stacking type catalyst layer is prepared on the surface of the water-retaining microporous layer on the anode side, and the fiber arrangement type catalyst layer is prepared on the surface of the proton exchange membrane on 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 other side of the proton exchange membrane can retain the protective shell with stronger mechanical property, thereby ensuring the mechanical strength of the catalyst layer substrate and effectively reducing the risk of damaging the fiber arrangement type catalyst layer in the preparation process.
4. The invention arranges the water-retaining microporous layer on the anode, which significantly relieves the performance attenuation of the membrane electrode under the low-humidification working condition.
Drawings
FIGS. 1(a) and 1(b) are graphs comparing the performance of a particulate stacked catalyst layer to a fiber-arranged catalyst layer under different humidification conditions;
FIG. 2 is a schematic diagram of a membrane electrode configuration;
FIG. 3 is a schematic view of the overall process flow for batch preparation of membrane electrodes;
FIG. 4 is a schematic view of a process flow for preparing an anode;
FIG. 5 is a schematic view of a process flow for preparing a cathode catalyst layer;
FIG. 6 is a scanning electron microscope photograph of the surface of the anode drainage microporous layer;
FIG. 7 is a scanning electron microscope photograph of the surface of the anode water-retaining microporous layer;
FIG. 8 is a scanning electron micrograph of a surface of a catalyst layer of an anode particle stacking type;
FIG. 9 is a scanning electron micrograph of a surface of a cathode fiber arrangement type catalyst layer;
FIG. 10 shows the results of polarization curve tests of membrane electrodes;
FIG. 11 shows the cyclic voltammetry test results for membrane electrodes;
fig. 12 is a comparison of the power generation performance of the membrane electrode under different humidification conditions.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
in order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The invention provides a novel structure of a fuel cell membrane electrode, aiming at the problems that the utilization rate of noble metal platinum 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.
A low platinum loading, mass-produced fuel cell membrane electrode, as shown in fig. 2, the structure of the membrane electrode configuration is, in order: the device comprises an anode gas diffusion layer, an anode 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;
notably, the anode microporous layer includes an anode water drainage microporous layer disposed near the anode gas diffusion layer, and an anode water retention microporous layer disposed near the anode particle stacked catalyst layer; the material components and the preparation process of the anode water-retention microporous layer are consistent with those of an anode particle stacked catalyst layer, and the anode water-retention microporous layer comprises preparation equipment, key parameters (such as temperature and the like) of the preparation process, and key parameters (such as selection of a solvent, mass ratio of porous carbon to perfluorosulfonic acid ionomer, total solid mass content of slurry and the like) of a slurry formula; the only difference is that the porous carbon in the anode catalyst layer carries platinum nanoparticles, while the porous carbon in the anode water-retention microporous layer does not carry platinum nanoparticles. The aim is to keep the microcosmic appearances of the anode catalyst layer and the anode water-retaining microporous layer consistent as much as possible, and effectively avoid the flooding caused by the pooling of liquid water at the interface between the anode catalyst layer and the anode water-retaining microporous layer. The arrangement scheme of the anode water-retention microporous layer is original.
Preparing an anode particle stacking type catalyst layer on the surface of the anode water-retention 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 of the surface of the proton exchange membrane with an anode ionomer layer, and integrally packaging the cathode microporous layer, the cathode gas diffusion layer and the membrane electrode according to the configuration sequence.
Each layer structure of the anode particle stacking type catalyst layer, the cathode fiber arrangement type catalyst layer and the cathode microporous layer is 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 includes four steps, 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 and the preparation of the cathode microporous layer and the gas diffusion layer are not in sequence, and can be carried out in parallel, and the membrane electrode assembly part is carried out 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 are not in sequence and can be carried out in parallel, and the preparation of the anode drainage microporous layer can be carried out after the two processes are finished.
1) Respectively preparing anode drainage microporous layer slurry, anode water retention microporous layer slurry and anode catalyst layer slurry;
the preparation of each slurry comprises the steps of weighing the raw materials according to the required proportion, mixing the raw materials of each slurry respectively, and uniformly dispersing to finish the preparation of each slurry.
The raw materials of the anode drainage microporous layer slurry comprise carbon powder, hydrophobic high molecular polymer and solvent; also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retention microporous layer slurry comprise porous carbon powder, perfluorinated sulfonic acid ionomer and a solvent; also comprises a surfactant and a pore-forming agent;
the raw materials of the anode catalyst layer slurry comprise a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer and a solvent; also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorinated sulfonic 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) on the anode gas diffusion layer material, preparing a covered anode drainage microporous layer, an anode water-retention microporous layer, an anode particle stacked catalyst layer and an anode ionomer layer in sequence;
the anode gas diffusion layer is a commercially available anode gas diffusion layer product directly purchased or a self-made anode gas diffusion layer. In this part of the work, the anode gas diffusion layer is cut to size and fixed in place in the anode drain microporous layer manufacturing apparatus in the proper orientation.
Methods of preparing the layers include spraying or coating, including specifically using an ultrasonic thermal spray device or a slot coating device.
And verifying the platinum load or the carbon load in each layer by detection, wherein the detection method comprises a weighing method, an X-ray fluorescence spectrometry and a thermogravimetric analysis.
Carbon in anode drainage microporous layerThe design value of the loading capacity is not lower than 0.5mg/cm2And not higher than 2mg/cm2。
The designed value of carbon loading in the anode water-retention microporous layer is not less than 0.1mg/cm2And not higher than 1mg/cm2。
The design value of platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm2And not higher than 0.2mg/cm2。
The thickness of the anode ionomer layer is not less than 0.1 μm and not more than 2 μm.
In the preparation process of the anode particle stacked catalyst layer, a preparation device consistent with the anode water-retention microporous layer is adopted to prepare the anode particle stacked catalyst layer on the surface of the anode water-retention microporous layer.
The anode ionomer layer slurry includes a commercial perfluorosulfonic acid ionomer dispersion product (e.g., Nafion D520, Nafion D2020, dupont, usa), a dilution or concentrate of a commercial perfluorosulfonic acid ionomer dispersion product, or a self-formulated perfluorosulfonic acid ionomer dispersion.
Cathode catalyst layer preparation
The cathode catalyst layer preparation process flow is shown in fig. 5. The preparation of the proton exchange membrane and the preparation of the cathode catalyst slurry are not in sequence and can be carried out in parallel, and the preparation of the cathode fiber arrangement type catalyst layer can be carried out after the two processes are finished.
1) Preparing cathode catalyst slurry: uniformly mixing and dispersing a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the composite material;
the perfluorosulfonic acid ionomer is solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high molecular spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) spinning by using the cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of the 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 a spinning device in a proper orientation on the other side of the proton exchange membrane; and fixed in place in the preparation apparatus for the cathode catalyst layer.
The spinning device comprises an electrostatic spinning device or a gas spinning device;
the design value of platinum loading capacity in the cathode fiber arrangement type catalyst layer is not less than 0.05mg/cm2And not higher than 0.5mg/cm2；
And verifying the platinum loading capacity in the cathode fiber arrangement type catalyst layer through detection, wherein the detection method comprises a weighing method, an X-ray fluorescence spectrometry and a thermogravimetric analysis.
Preparation of cathode microporous layer and gas diffusion layer
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.
The cathode microporous layer is of a single-layer structure with uniform materials or a multi-layer composite structure with less than 3 layers. In addition, the cathode microporous layer and the cathode gas diffusion layer must be trimmed to size during this portion of the operation.
Membrane electrode assembly
In the membrane electrode assembly process, according to the membrane electrode configuration shown in fig. 2, it is ensured that the respective structures are arranged in the order of "anode gas diffusion layer-anode water drainage microporous layer-anode water retention microporous layer-anode particle stacking type catalyst layer-anode ionomer layer-proton exchange membrane-cathode fiber arrangement type catalyst layer-cathode microporous layer-cathode gas diffusion layer" shown in fig. 2, and the respective structures are 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 uncovered, and sealing frames with proper shapes and thicknesses are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer. After the steps are completed, the membrane electrode is subjected to hot-pressing packaging by using proper pressure and temperature, and the membrane electrode assembly work is completed.
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, the hydrophobic property of the water-draining microporous layer near the gas diffusion layer is stronger, and the hydrophobic property of the water-retaining microporous layer near the anode catalyst layer is relatively weaker. The cathode directly adopts a commercialized product with a gas diffusion layer and a microporous layer, and the model is H23-cx653 of Germany Kedebao 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 are not in sequence and can be carried out in parallel, and the preparation of the anode drainage microporous layer can be carried out after the two processes are finished.
1) Respectively preparing anode drainage microporous layer slurry, anode water retention microporous layer slurry and anode catalyst layer slurry;
the preparation process of each slurry comprises the steps of weighing raw materials according to the required proportion, mixing the raw materials of each slurry respectively, carrying out ultrasonic dispersion for 0.5 hour, carrying out high-speed shearing dispersion for 1 hour, and carrying out secondary ultrasonic dispersion for 0.5 hour;
the anode drainage microporous layer slurry is prepared from Vulcan XC-72 type conductive carbon powder of CABOT Company (CABOT), polytetrafluoroethylene powder and an 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 raw materials of the anode water-retention microporous layer slurry are KetjenblackECP-600JD conductive carbon powder of Nippon LION king company (LION), Nafion D520 perfluorinated sulfonic acid ionomer dispersion liquid of Dupont company, deionized water and an isopropanol solvent, wherein the mass ratio of the carbon powder to the perfluorinated sulfonic acid ionomer is 1:0.7, the mass ratio of water to the isopropanol is 1:5, and the total solid mass content in the anode water-retention microporous layer slurry is 2.5%.
The raw materials of the anode catalyst layer slurry are a Pt/C catalyst (wherein the Pt mass content is 40%, and the carbon carrier is conductive carbon powder of Ketjenblack ECP-600 JD), deionized water, Nafion D520 type perfluorinated sulfonic acid ionomer dispersion liquid of Dupont in America 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) A commercial anode gas diffusion layer product, which was directly purchased, was cut to an appropriate size and fixed in an appropriate position in a preparation apparatus of an anode drainage microporous layer in an appropriate orientation, and an anode drainage microporous layer, an anode water retention microporous layer, an anode particle stacked catalyst layer, and an anode ionomer layer, which were coated, were sequentially prepared using an ultrasonic thermal spray method. The ultrasonic thermal spraying equipment adopts a PRISM-400BT type product of USI company of America, and the spraying temperature is 100 ℃.
The anode ionomer layer spray slurry was prepared directly from nafion d520 perfluorosulfonic acid ionomer dispersion, Dupont, usa, and had an average thickness of 0.3 μm.
And detecting and verifying the platinum loading or the carbon loading in each layer by a weighing method, an X-ray fluorescence spectrometry method or a thermogravimetric analysis method.
Wherein the total carbon content of the anode drainage microporous layer after the preparation is 1.2mg/cm2The typical surface topography is shown in fig. 6.
The total carbon content of the anode water-retention microporous layer after the preparation is 0.25mg/cm2The typical surface topography is shown in fig. 7.
The total platinum content after the preparation of the anode particle stacked catalyst layer was 0.05mg/cm2The typical surface topography is shown in fig. 8.
The preparation scheme ensures that the microscopic appearances of the anode particle stacked catalyst layer and the anode water-retention microporous layer are basically consistent, and can effectively avoid the flooding caused by the pooling of liquid water at the interface between the anode catalyst layer and the anode water-retention microporous layer.
Cathode catalyst layer preparation
The cathode catalyst layer preparation process flow is shown in fig. 5. The preparation of the proton exchange membrane and the preparation of the cathode catalyst slurry are not in sequence and can be carried out in parallel, and the preparation of the cathode fiber arrangement type catalyst layer can be carried out after the two processes are finished.
1) Preparing cathode catalyst slurry: the 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 the United states; wherein the mass ratio of the Pt/C catalyst to the perfluorosulfonic acid ionomer is 2.5:1, the mass ratio of water to isopropanol is 1:3, the mass ratio of polyacrylic acid to the 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 cathode fiber arrangement type catalyst layer spinning slurry comprises the steps of firstly stirring for 12 hours by using magnetons, and then shearing and dispersing for 1 hour at a high speed.
2) Spinning by using the cathode catalyst slurry, and preparing a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane;
the cathode fiber arrangement type catalyst layer is prepared by adopting an electrostatic spinning method, the electrostatic spinning equipment adopts Elite series products of Beijing Yongkang Leye scientific and technological development Limited company, the spinning temperature is set to be 35 ℃, the humidity is set to be RH 15%, the positive high voltage is set to be 6kV, and the negative high voltage is set to be-3 kV.
The proton exchange membrane is 15 μm thick and is available from Gore, Inc. (Gore) of America
Membrane series products. After the proton exchange membrane is cut to a proper size, the proton exchange membrane is fixed on a roller filament collecting device of electrostatic spinning equipment, one surface of a protective shell, which is covered, faces to a roller, the nanofiber is directly collected by adopting a roller filament 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 15 cm.
Detecting and verifying the platinum loading capacity in the cathode fiber arrangement type catalyst layer by a weighing method, an X-ray fluorescence spectrometry method or a thermogravimetric analysis method to obtain the catalystThe total platinum content after the preparation of the cathode fiber arrangement type catalyst layer is 0.075mg/cm2The typical surface topography is shown in fig. 9.
Preparation of cathode microporous layer and gas diffusion layer
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 model of Germany Kedebao company (Freudenberg). In this part of the work, the cathode microporous layer and cathode gas diffusion layer also need to be trimmed to size.
Membrane electrode assembly
In the process of assembling the membrane electrode, the protective shell originally covered on the proton exchange membrane is completely uncovered, sealing gaskets with proper shapes and 135 micrometers in thickness are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer, then the hot-pressing pressure is set to be 1 ton, the temperature is 120 ℃, and the pressure maintaining time is 30 s. According to the membrane electrode configuration shown in fig. 2, it is ensured that the respective structures are arranged in the order of "anode gas diffusion layer-anode drain microporous layer-anode water retention microporous layer-anode particle stacked catalyst layer-anode ionomer layer-proton exchange membrane-cathode fiber arrangement catalyst layer-cathode microporous layer-cathode gas diffusion layer" shown in fig. 2, and aligned with the respective structures, and hot press packaging is performed.
The low platinum load fuel cell membrane electrode prepared according to the process of the embodiment shows better performance and higher utilization rate of noble metal platinum. Fig. 10 shows the polarization curve test results of the membrane electrode under the hydrogen/air test conditions 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/cm2Therefore, the total platinum dosage of the cathode and the anode of the membrane electrode is lower than 0.125g/kW, wherein the cathode platinum dosage is lower than 0.075 g/kW.
Fig. 11 shows the cyclic voltammetry test results of the membrane electrode. As shown in the figure, the electrochemical active area of the membrane electrode cathode fiber arrangement type catalyst layer is 74.19m under the condition of 25 DEG C2/gptThe higher utilization rate of noble metal platinum at the cathode is that the total platinum dosage of the membrane electrode is lowerThe main reason for (1).
Due to the arrangement of the anode water-retention microporous layer, the performance attenuation of the membrane electrode under the low-humidification working condition is effectively controlled, as shown in fig. 12, if the relative humidity of the anode humidification is kept to be 100%, even if the relative humidity of the cathode humidification is reduced from 100% to 0%, the performance of the membrane electrode is not obviously reduced; continuously keeping the relative humidity of cathode humidification at 0%, reducing the relative humidity of anode humidification from 100% to 30%, and the performance reduction of the membrane electrode is still within an acceptable range; when the relative humidity of the cathode and the anode is reduced to 0%, the stability of the membrane electrode test is reduced, and the phenomenon of serious membrane dryness occurs in a low current density area, the performance is reduced seriously, but partial recovery is realized in a high current density area. The above phenomena all powerfully prove the function of the anode water-retention microporous layer.
Claims (10)
1. A fuel cell membrane electrode with low platinum loading and mass production is characterized in that the structure of the membrane electrode configuration sequentially comprises: an anode gas diffusion layer, an anode 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;
the anode microporous layer comprises an anode drainage microporous layer arranged close to the anode gas diffusion layer and an anode water retention microporous layer arranged close to the anode particle stacking type catalyst layer;
preparing an anode particle stacked catalyst layer on the surface of the anode water-retention microporous layer, and preparing a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane.
2. The low platinum load, mass produced fuel cell membrane electrode of claim 1,
the components of the anode water-retention microporous layer do not contain platinum nanoparticles, and the components of the anode particle stacked catalyst layer contain platinum nanoparticles; the anode water-retention microporous layer and the anode particle stacked catalyst layer have the same other components and structures.
3. The low platinum load, mass produced fuel cell membrane electrode of claim 1,
the carbon loading in the anode drainage microporous layer is not less than 0.5mg/cm2And not higher than 2mg/cm2；
The carbon loading capacity in the anode water-retention microporous layer is not less than 0.1mg/cm2And not higher than 1mg/cm2；
The platinum loading in the anode particle stacked catalyst layer is not less than 0.02mg/cm2And not higher than 0.2mg/cm2；
The platinum loading capacity in the cathode fiber arrangement type catalyst layer is not less than 0.05mg/cm2And not higher than 0.5mg/cm2；
The thickness of the anodic ionomer layer is not less than 0.1 microns and not more than 2 microns.
4. The low platinum loading, mass produced fuel cell membrane electrode of claim 1 wherein each of said anode particle stacked catalyst layer, cathode fiber arranged catalyst layer and cathode microporous layer is a uniform single layer structure or a multi-layer structure of no more than 3 layers.
5. A method for preparing fuel cell membrane electrode with low platinum loading and mass production, which is characterized in that,
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 gas diffusion layer can be simultaneously carried out, and finally the membrane electrode assembly part is carried out.
6. The method of making a low platinum loading, mass produced fuel cell membrane electrode according to claim 5,
the preparation process of the anode comprises the following steps:
1) respectively preparing anode drainage microporous layer slurry, anode water retention 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 composite material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode water-retention microporous layer slurry comprise porous carbon powder, perfluorinated sulfonic acid ionomer and a solvent; further, the material also comprises a surfactant and a pore-forming agent;
the raw materials of the anode catalyst layer slurry comprise a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer and a solvent; further, the material also comprises a surfactant and a pore-forming agent;
the hydrophobic high molecular polymer and the perfluorinated sulfonic 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) on the anode gas diffusion layer material, preparing an anode drainage microporous layer, an anode water-retention microporous layer, an anode particle stacked catalyst layer and an anode ionomer layer in turn; the anode ionomer layer slurry is a perfluorosulfonic acid ionomer dispersion.
7. The method of making a low platinum loading, mass produced fuel cell membrane electrode 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 a Pt/C catalyst, deionized water, a perfluorinated sulfonic acid ionomer, an organic solvent and a high-molecular spinning auxiliary agent to obtain the composite material;
the perfluorosulfonic acid ionomer is solid or perfluorosulfonic acid ionomer dispersion;
the organic solvent comprises one or more of ethanol, isopropanol, dimethylformamide and dimethyl sulfoxide;
the high molecular spinning auxiliary agent comprises polyacrylic acid, polyvinylidene fluoride, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile or polymethyl methacrylate;
2) and spinning by using the cathode catalyst slurry to prepare a cathode fiber arrangement type catalyst layer on the surface of the proton exchange membrane.
8. The method of making a low platinum loading, mass produced fuel cell membrane electrode of claim 5, wherein said membrane electrode assembly process is: the protective shell originally covered on the proton exchange membrane is completely uncovered before packaging, all layers are aligned according to the configuration of the membrane electrode, and the membrane electrode is subjected to hot-press packaging after sealing frames are respectively arranged on the outer sides of the cathode gas diffusion layer and the anode gas diffusion layer.
9. The method of making a low platinum loading, mass produced fuel cell membrane electrode assembly according to claim 6 wherein said method of making each layer comprises spraying or coating, particularly using an ultrasonic thermal spraying device or a slot coating device.
10. The method of making a low platinum loading, mass produced fuel cell membrane electrode assembly according to claim 7, wherein said spinning apparatus comprises an electrospinning apparatus or a gas spinning apparatus.
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