CN114520339A - CCM for fuel cell and preparation method thereof - Google Patents

CCM for fuel cell and preparation method thereof Download PDF

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Publication number
CN114520339A
CN114520339A CN202210093007.7A CN202210093007A CN114520339A CN 114520339 A CN114520339 A CN 114520339A CN 202210093007 A CN202210093007 A CN 202210093007A CN 114520339 A CN114520339 A CN 114520339A
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platinum
carbon
layer
ionic polymer
catalyst
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沈新龙
曹寅亮
李伯球
方蕾
范峰强
杨光华
孙基文
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Zhejiang Tianneng Hydrogen Energy Technology Co ltd
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Zhejiang Tianneng Hydrogen Energy Technology Co ltd
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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
    • H01M4/90—Selection of catalytic material
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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 CCM for a fuel cell and a preparation method thereof, relating to the field of fuel cells. A CCM for a fuel cell comprises a proton exchange membrane and catalyst layers positioned on two sides of the proton exchange membrane, wherein the catalyst layers are divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane to the outside. The CCM for the fuel cell has the advantages of good drainage effect, good degradation loss resistance and good durability, and the preparation method is simple to operate and is suitable for batch production and laboratory operation.

Description

CCM for fuel cell and preparation method thereof
Technical Field
The invention relates to the field of fuel cells, in particular to a CCM for a fuel cell and a preparation method thereof.
Background
A Fuel Cell (Fuel Cell) is an electrochemical power generation device that electrochemically converts chemical energy directly into electrical energy, unlike a conventional battery. The method is not limited by Carnot cycle because of no hot air machine process, has high energy conversion efficiency (40-60 percent), is environment-friendly, and hardly discharges nitrogen and sulfur oxides. Fuel cells have been the focus of research in various countries around the world due to their excellent performance, and have played a great role in power generation, mobile power supplies, and vehicle power supplies. The research on fuel cell automobiles is increasingly intensive, but the commercialization of the fuel cell automobiles still has the technical bottleneck problem, a large amount of water generated by the fuel cell during operation is easy to enter electrode holes, and is difficult to drain to cause local flooding by covering the surface of a catalyst layer, so that the effective contact of reaction gas and a catalyst is prevented, and the performance of an electrode is reduced. The noble metal catalyst of the catalyst layer can be degraded and lost after long-time operation, so that the effective catalytic area is reduced, and the performance is reduced.
The fuel cell chip is a catalyst/proton exchange membrane module, which is prepared by coating fuel cell catalyst on two sides of a proton exchange membrane, and is called CCM (catalyst coated membrane) for short. CCM has the following advantages compared to conventional membrane electrode assembly (mea) prepared by coating a catalyst on the surface of a gas diffusion layer (i.e., carbon paper or carbon cloth): 1) the catalyst layer is ultra-thin, the catalytic efficiency of the catalyst is greatly improved, and the loading capacity of the Pt noble metal catalyst is reduced (generally reduced to 0.4-0.6 mg/cm)2The following); 2) the proton exchange membrane can be ultra-thin, the surface conductance of the membrane is improved, and the dosage of the membrane is also reduced; 3) short activation time of the battery, quick electrochemical response and the like. Therefore, CCM technology is considered the second revolution in fuel cell membrane electrode technology.
Patent application No. CN102325602B discloses a Catalyst Coated Membrane (CCM) and a catalyst membrane/catalyst layer for alkaline membrane fuel cells and a method for making the same, based on a fuel cell cathode catalyst layer without a supported metal particle layer, with the advantage of intrinsic stability over catalyst layers based on carbon supported metal particles. Alkaline membrane fuel cells designed using silver cathode catalysts include a catalytic layer comprising silver metal nano-particles and an anion conducting ionomer. Silver metal nano-particles are mixed with an ionomer solution to form a catalyst ink, which is applied to an alkaline membrane to form an ultra-thin cathode catalyst layer on the surface of the membrane.
The patent application with the publication number of CN112310413A discloses a gas diffusion layer, a preparation method and application thereof, wherein the gas diffusion layer comprises a support layer, and a composite carbon material diffusion layer and a microporous layer which are sequentially arranged on the surface of the support layer; the support layer is made of porous materials, and the composite carbon material diffusion layer comprises carbon nanotubes and carbon fibers. The supporting layer has higher mechanical strength, and can be used as a frame base of a current collecting layer and a diffusion layer; the carbon nanotube and the carbon fiber are mixed, the carbon fiber is used as a substrate framework, the carbon nanotube is used as a filler of the framework, the requirement of high air permeability of the gas diffusion layer is met, and the carbon nanotube has high mechanical strength; the microporous layer can fill pores with different sizes of the diffusion layer, and can slow down the unevenness of the diffusion layer, thereby realizing redistribution of water and reaction gas in a flow field and a catalysis layer, increasing the conductivity and prolonging the service life of the battery.
Therefore, CCMs for fuel cells having good durability against degradation loss have become a new direction of research.
Disclosure of Invention
The invention aims to provide a CCM for a fuel cell with good drainage effect and good degradation loss resistance and durability and a preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows: a CCM for fuel cells comprises a proton exchange membrane, catalytic layers adhered to both sides of the membrane, wherein the cathode catalytic layer comprises a hydrophilic low platinum content catalytic layer, a hydrophobic high performance high platinum content catalytic layer, and a hydrophobic low platinum content catalytic layer. The method is characterized in that: the catalyst layer has a hydrophilic and hydrophobic property to form a gradient structure, which is beneficial to drainage and airflow distribution, and the low-platinum multi-carbon catalyst on both sides of the catalyst layer is resistant to degradation and loss.
The invention provides a CCM for a fuel cell, which comprises a proton exchange membrane and catalyst layers positioned at two sides of the proton exchange membrane, wherein the catalyst layers are divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane to the outside;
the hydrophilic layer comprises a platinum-carbon catalyst a, an ionic polymer and a hydrophilic agent, and the mass ratio of carbon, the ionic polymer and the hydrophilic agent in the platinum-carbon catalyst a is 1: 0.1-10;
the first hydrophobic layer comprises a platinum-carbon catalyst b, an ionic polymer and a hydrophobic agent, and the mass ratio of carbon, the ionic polymer and the hydrophobic agent in the platinum-carbon catalyst b is 1: 0.1-10: 0.5-10;
the second hydrophobic layer comprises a platinum carbon catalyst c, an ionic polymer and a hydrophobic agent, and the mass ratio of carbon, the ionic polymer and the hydrophobic agent in the platinum carbon catalyst c is 1: 0.1-10.
Specifically, the platinum mass content of the platinum-carbon catalyst a in the hydrophilic layer is 20%, the platinum mass content of the platinum-carbon catalyst b in the first hydrophobic layer is 50%, and the platinum mass content of the platinum-carbon catalyst c in the second hydrophobic layer is 20%.
Preferably, the ionic polymer is dupont D520.
Preferably, the hydrophilic agent is a threeway D83 solution.
Preferably, the hydrophobic agent is a polytetrafluoroethylene solution.
The structure of CCM is shown in fig. 4, in which the hydrophilic layer contains a hydrophilic agent to facilitate transfer of the generated water near the proton exchange membrane side in the hydrophilic layer, and when the hydrophilic layer is saturated with water, moisture is transferred to the first hydrophobic layer and the hydrophilic layer, and the first hydrophobic layer to the hydrophilic layer contain a hydrophobic solvent, so that moisture can be rapidly and smoothly discharged from the catalytic layer. The catalyst platinum content in the hydrophilic layer and the second hydrophobic layer is low, when the carbon carrier content is high and the specific surface area of graphitization treatment is low, corrosion, oxidation and attenuation can be resisted, the agglomeration and loss of noble metal platinum can be reduced due to the low platinum content in the oxidation attenuation, the first hydrophobic layer with high platinum content, high specific surface area and high performance is protected to be more durable, and therefore the whole electrode has high durability and long service life.
The invention also provides a preparation method of the CCM for the fuel cell, which comprises the following steps:
(1) mixing a platinum-carbon catalyst a with an ionic polymer, and adding a hydrophilic agent to obtain hydrophilic layer slurry;
(2) mixing a platinum-carbon catalyst b and an ionic polymer, and adding a hydrophobic agent to obtain first hydrophobic layer slurry;
(3) mixing the platinum-carbon catalyst c with the ionic polymer, and adding a hydrophobic agent to obtain second hydrophobic layer slurry;
(4) compounding the three kinds of slurry on two sides of a proton exchange membrane, wherein the compounding sequence is that a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on one side of the proton exchange membrane outwards; thereby obtaining a CCM for a fuel cell.
Preferably, the total thickness of the three layers is 24 μm, and the thickness of the three layers from the proton membrane to the outside is 6 μm, 14 μm, 4 μm, respectively. This thickness ratio works best, with larger deviations being less effective.
Specifically, the platinum-carbon catalyst a in the step (1) is TANAKA brand TEC10EA20E, and the mass content of platinum is 20%; the platinum-carbon catalyst b in the step (2) is TANAKA brand TEC10E50E, and the mass content of platinum is 50%; the platinum-carbon catalyst c in the step (3) is EC10VA20E of TANAKA brand, and the platinum mass content is 20%.
Preferably, the ionic polymer is dupont D520.
Preferably, the hydrophilic agent is Suwei D83 solution, and the hydrophobic agent is polytetrafluoroethylene solution.
Specifically, in the step (1), the mass ratio of the carbon, the ionic polymer and the hydrophilic agent in the platinum-carbon catalyst a is 1: 0.1-10;
in the step (2), the mass ratio of the carbon in the platinum-carbon catalyst b, the ionic polymer and the hydrophobic agent is 1: 0.1-10: 0.5-10;
in the step (3), the mass ratio of the platinum-carbon catalyst c, the ionic polymer and the hydrophobing agent is 1: 0.1-10.
Has the advantages that:
(1) the invention provides a CCM for a fuel cell, which has good drainage effect and good degradation loss resistance and durability. The catalyst layer is divided into three layers, the middle layer has high performance, the two side layers have good durability, and the structure improves the performance and the durability of the whole CCM. The catalyst layer contains a hydrophilic layer close to the proton membrane side, so that a certain amount of moisture can be retained, the proton membrane can be kept wet, the proton conductivity is improved, the impedance is reduced, the catalyst layer is suitable for a dry environment, and good performance output is kept. The hydrophobic layer is arranged on the outer side of the catalyst layer, so that moisture generated in work can be well discharged, the gas mass transfer effect is improved, and the electrical property is improved.
(4) The preparation method disclosed by the patent is simple to operate, can be applied to a conventional preparation process, does not need a special process, and is suitable for batch production and laboratory operation.
Drawings
FIG. 1 is a graph showing the change in voltage under the battery life test in comparative examples 1 and 2; wherein A is a voltage change diagram under the battery life test in comparative example 1; wherein B is a voltage change chart under the battery life test in comparative example 2.
FIG. 2 is a graph showing the change in voltage under the battery life test in examples 1 and 2; wherein, A is a voltage change diagram under the battery life test in the embodiment 1; wherein, B is a voltage variation graph under the battery life test in example 2.
FIG. 3 is a graph showing the change in voltage under the battery life test in examples 3 and 4; wherein, a is a voltage variation graph under the battery life test in the embodiment 3; wherein, B is a voltage variation graph under the battery life test in example 4.
FIG. 4 is a view of a CCM structure; wherein 1 represents a proton exchange membrane; 2 represents 20% platinum content catalyst particles; 3 represents an ionic polymer containing a hydrophilic agent; 4 represents an ionic polymer containing a hydrophobic agent; 5 represents 20% platinum content catalyst particles; 6 represents 50% platinum content catalyst particles; 7 represents a second hydrophobic layer; 8 represents a first hydrophobic layer; and 9 represents a hydrophilic layer.
Detailed Description
Example 1
(1) Preparing hydrophilic layer slurry:
1) weighing 20% of TEC10EA20E of noble metal catalyst TANAKA brand (noble metal group in field) with platinum content and high durability for graphitization, and stirring and mixing with 5% of DuPont d520 ionic polymer solution, wherein the mass ratio of carbon in the TEC10EA20E is as follows: the ionic polymer is 1: 1, and the stirring time is 30 min;
2) then 8% by mass of hydrophilic solvent Suwei D83 solution (brand is solvay, model is D83-24B) is added, and the mass ratio of carbon in the TEC10EA20E is as follows: stirring the hydrophilic agent at a ratio of 1: 2 for 20 min;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing a first hydrophobic layer slurry:
1) weighing 50% of platinum content and high specific surface area noble metal catalyst TANAKA brand TEC10E50E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 1, and the stirring time is 30 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 2;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(3) preparing second hydrophobic layer slurry:
1) weighing 20% of platinum content, durable high-surface-area noble metal catalyst TANAKA brand TEC10VA20E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10VA20E is 1: 1, and stirring time is 20 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10VA20E to the hydrophobing agent solution is 1: 0.8;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(4) preparing a catalyst layer:
respectively and uniformly spraying the uniformly dispersed cathode and anode catalyst layer slurry on two sides of a proton exchange membrane M765.08 by using ultrasonic spraying equipment to form cathode and anode catalyst layers, wherein the side of the proton exchange membrane is sequentially hydrophilic outwardsThe platinum loading capacity of the catalyst layer is controlled through the calculation of the platinum content of the catalyst layer slurry, and the platinum loading capacity in the catalyst layer is verified through weighing. The spraying process parameters are as follows: slurry inlet flow rate of 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading capacity of the cathode platinum is 0.4mg/cm2。
(5) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with the flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
Example 2
(1) Preparing hydrophilic layer slurry:
1) weighing 20% of platinum content, and stirring and mixing a graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with a DuPont d520 ionic polymer solution, wherein the mass ratio of carbon to ionic polymer in the TEC10EA20E is 1: 0.7, and the stirring time is 20 min;
2) then adding a Suwei D83 solution with the mass percent of hydrophilic solvent being 8%, wherein the mass ratio of carbon to hydrophilic agent in the TEC10EA20E is 1: 2, and stirring for 20 min;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing first hydrophobic layer slurry:
1) weighing 50% of platinum content and high specific surface area noble metal catalyst TANAKA brand TEC10E50E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 0.6, and stirring time is 30 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 2;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(3) preparing second hydrophobic layer slurry:
1) weighing 20% of platinum content, durable high-surface-area noble metal catalyst TANAKA brand TEC10VA20E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10VA20E is 1: 1, and stirring time is 20 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan gold D210C, and stirring for 20min, wherein the mass ratio of carbon in TEC10VA20E to the hydrophobing agent solution is 1: 2;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(4) preparing a catalytic layer:
and respectively and uniformly spraying the uniformly dispersed cathode and anode catalyst layer slurry on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalyst layer, wherein a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the side of the proton exchange membrane outwards, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurry, and the platinum loading capacity in the catalyst layer is verified by weighing. The spraying process parameters are as follows: slurry inlet flow rate of 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: at 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading amount of the cathode platinum is 0.4mg/cm2。
(5) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
Example 3
(1) Preparing hydrophilic layer slurry:
1) weighing 20% of platinum content, and stirring and mixing a graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with a DuPont d520 ionic polymer solution, wherein the mass ratio of carbon to ionic polymer in the TEC10EA20E is 1: 10, and the stirring time is 40 min;
2) then adding a Suwei D83 solution with the mass percent of hydrophilic solvent being 8%, wherein the mass ratio of carbon to hydrophilic agent in the TEC10EA20E is 1: 10, and stirring for 20 min;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing a first hydrophobic layer slurry:
1) weighing 50% of platinum content, high specific surface area noble metal catalyst TANAKA brand TEC10E50E, and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 10, and stirring time is 40 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 40min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 10;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(3) preparing a second hydrophobic layer slurry:
1) weighing 20% of platinum content, durable high-surface-area noble metal catalyst TANAKA brand TEC10VA20E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10VA20E is 1: 10, and stirring time is 40 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 40min, wherein the mass ratio of carbon in the TEC10VA20E to the hydrophobing agent solution is 1: 10;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(4) preparing a catalytic layer:
the uniformly dispersed cathode and anode catalyst layer slurry is respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalyst layer, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the side of the proton exchange membrane from the side to the outside, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurry, and the platinum loading capacity in the catalyst layer is verified by weighing. The spraying process parameters are as follows: slurry feed flow rate 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading amount of the cathode platinum is 0.4mg/cm2。
(5) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
Example 4
(1) Preparing hydrophilic layer slurry:
1) weighing 20% of platinum content, and stirring and mixing a graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with a DuPont d520 ionic polymer solution, wherein the mass ratio of carbon to ionic polymer in the TEC10EA20E is 1: 0.1, and the stirring time is 10 min;
2) then adding a Suwei D83 solution with the mass percent of hydrophilic solvent being 8%, wherein the mass ratio of carbon to hydrophilic agent in the TEC10EA20E is 1: 0.1, and stirring for 10 min;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing a first hydrophobic layer slurry:
1) weighing 50% of platinum content and high specific surface area noble metal catalyst TANAKA brand TEC10E50E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 0.1, and stirring time is 10 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 10min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 0.5;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(3) preparing a second hydrophobic layer slurry:
1) weighing 20% of platinum content, durable high-surface-area noble metal catalyst TANAKA brand TEC10VA20E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10VA20E is 1: 0.1, and the stirring time is 10 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10VA20E to the hydrophobing agent solvent is 1: 0.1;
3) then carrying out integral ultrasonic homogenization for 10min for later use;
(4) preparing a catalytic layer:
the uniformly dispersed cathode and anode catalyst layer slurry is respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalyst layer, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the side of the proton exchange membrane from the side to the outside, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurry, and the platinum loading capacity in the catalyst layer is verified by weighing. The spraying process parameters are as follows: slurry inlet flow rate of 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: at 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading amount of the cathode platinum is 0.4mg/cm2。
(5) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
Comparative example 1
(1) Preparing a first hydrophobic layer slurry:
1) weighing 50% of platinum content and high specific surface area noble metal catalyst TANAKA brand TEC10E50E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 1, and the stirring time is 30 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 2;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing a catalytic layer:
and respectively and uniformly spraying the uniformly dispersed cathode and anode catalyst layer slurry on two sides of a Goll proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalyst layer, calculating and controlling the platinum loading capacity of the catalyst layer through the platinum content of the catalyst layer slurry, and verifying the platinum loading capacity in the catalyst layer by weighing. The spraying process parameters are as follows: pulp and its production processFeed inlet flow rate is 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading amount of the cathode platinum is 0.4mg/cm2。
(3) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
Comparative example 2
(1) Preparing hydrophilic layer slurry:
1) weighing 20% of platinum content, and stirring and mixing a graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with a DuPont d520 ionic polymer solution with the mass percent of 5%, wherein the mass ratio of carbon to ionic polymer in the TEC10EA20E is 1: 1, and the stirring time is 30 min;
2) then adding a Suwei D83 solution with the mass percent of hydrophilic solvent being 8%, wherein the mass ratio of carbon to hydrophilic agent in the TEC10EA20E is 1: 2, and stirring for 20 min;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(2) preparing a first hydrophobic layer slurry:
1) weighing 50% of platinum content and high specific surface area noble metal catalyst TANAKA brand TEC10E50E and 5% of DuPont d520 ionic polymer solution, stirring and mixing, wherein the mass ratio of carbon to ionic polymer in the TEC10E50E is 1: 1, and the stirring time is 30 min;
2) then adding a PTFE solution (the mass percentage is 60%) of a hydrophobing agent solution Japan Dajin D210C, and stirring for 20min, wherein the mass ratio of carbon in the TEC10E50E to the hydrophobing agent solution is 1: 2;
3) then carrying out integral ultrasonic homogenization for 40min for later use;
(3) preparing a catalytic layer:
respectively and uniformly spraying the uniformly dispersed cathode and anode catalyst layer slurry on two sides of a proton exchange membrane M765.08 by using ultrasonic spraying equipment to form cathode and anode catalyst layers, wherein the hydrophilic layer is arranged on one side close to the proton exchange membrane and passes through the catalyst layersThe platinum loading of the catalytic layer is controlled by calculating the platinum content of the slurry, and the platinum loading of the catalytic layer is verified by weighing. The spraying process parameters are as follows: slurry inlet flow rate of 0.8mL/min, nozzle speed: 120mm/min, height of the nozzle: 35mm, drying temperature: 80 ℃. Wherein the loading capacity of the anode platinum is 0.05mg/cm2The loading amount of the cathode platinum is 0.4mg/cm2。
(4) And (3) heat treatment:
putting the proton exchange membrane compounded with the catalyst slurry on two sides into a hot press with flatness of 1-5 filaments at 110 ℃ and 5kg/cm2The CCM for the fuel cell was obtained after the conditioning for 60 min.
The prepared CCM undergoes the attenuation result of cyclic voltammetry test as follows:
after 90 hours, the materials respectively attenuate by 3.11 percent, 5.26 percent and 12.65 percent under the conditions of 300, 800 and 1200 electric densities
The fuel cells prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to cyclic voltammetry test using CCM.
The results of the tests for decay at 300, 800, 1200 current densities after 50 hours are shown in table 1 and fig. 1-3.
TABLE 1
Sample numbering 300 electrical density attenuation% Attenuation of 800 watt-hour 1200 electrical density attenuation%
Comparative example 1 2.36 4.43 8.02
Comparative example 2 1.41 3.5 5.05
Example 1 1.26 1.27 1.51
Example 2 1.39 1.58 2.13
Example 3 1.88 2.14 2.28
Example 4 1.3 2.91 3.11
From the results, it is understood that the durability of the CCM produced by the method of the present invention is greatly improved.

Claims (10)

1. A CCM for a fuel cell comprises a proton exchange membrane and catalyst layers positioned at two sides of the proton exchange membrane, and is characterized in that the catalyst layers are divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane to the outside;
the hydrophilic layer comprises a platinum-carbon catalyst a, an ionic polymer and a hydrophilic agent, and the mass ratio of carbon, the ionic polymer and the hydrophilic agent in the platinum-carbon catalyst a is 1: 0.1-10;
the first hydrophobic layer comprises a platinum-carbon catalyst b, an ionic polymer and a hydrophobic agent, and the mass ratio of carbon, the ionic polymer and the hydrophobic agent in the platinum-carbon catalyst b is 1: 0.1-10: 0.5-10;
the second hydrophobic layer comprises a platinum carbon catalyst c, an ionic polymer and a hydrophobic agent, and the mass ratio of carbon, the ionic polymer and the hydrophobic agent in the platinum carbon catalyst c is 1: 0.1-10.
2. The CCM for a fuel cell according to claim 1, wherein the platinum mass content of the platinum carbon catalyst a in the hydrophilic layer is 20%, the platinum mass content of the platinum carbon catalyst b in the first hydrophobic layer is 50%, and the platinum mass content of the platinum carbon catalyst c in the second hydrophobic layer is 20%.
3. The CCM for a fuel cell of claim 1 wherein the ionomer is dupont D520.
4. The fuel cell CCM of claim 1 wherein said hydrophilic agent is a threeway D83 solution.
5. The fuel cell CCM of claim 1 wherein the water repellant is a polytetrafluoroethylene solution.
6. A method of producing a CCM for a fuel cell as defined in any one of claims 1 to 5, comprising the steps of:
(1) mixing a platinum-carbon catalyst a with an ionic polymer, and adding a hydrophilic agent to obtain hydrophilic layer slurry;
(2) mixing a platinum-carbon catalyst b and an ionic polymer, and adding a hydrophobic agent to obtain first hydrophobic layer slurry;
(3) mixing the platinum-carbon catalyst c with the ionic polymer, and adding a hydrophobic agent to obtain second hydrophobic layer slurry;
(4) compounding the three kinds of slurry on two sides of a proton exchange membrane, wherein the compounding sequence is that a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on one side of the proton exchange membrane outwards; thereby obtaining a CCM for a fuel cell.
7. The method of claim 6, wherein the platinum-carbon catalyst a in step (1) is TANAKA brand TEC10EA20E and the platinum content is 20% by mass; the platinum-carbon catalyst b in the step (2) is TANAKA brand TEC10E50E, and the mass content of platinum is 50%; the platinum-carbon catalyst c in the step (3) is TANAKA brand TEC10VA20E, and the mass content of platinum is 20%.
8. The method of claim 6, wherein the ionic polymer is DuPont D520.
9. The method of claim 6, wherein the hydrophilic agent is Suwei D83 solution and the hydrophobic agent is polytetrafluoroethylene solution.
10. The preparation method according to claim 6, wherein in the step (1), the mass ratio of the carbon, the ionic polymer and the hydrophilic agent in the platinum-carbon catalyst a is 1: 0.1-10;
in the step (2), the mass ratio of the carbon in the platinum-carbon catalyst b, the ionic polymer and the hydrophobic agent is 1: 0.1-10: 0.5-10;
in the step (3), the mass ratio of the platinum-carbon catalyst c, the ionic polymer and the hydrophobing agent is 1: 0.1-10.
CN202210093007.7A 2022-01-26 2022-01-26 CCM for fuel cell and preparation method thereof Pending CN114520339A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1612381A (en) * 2003-10-27 2005-05-04 中国科学院大连化学物理研究所 Membrane electrode structure for proton exchange membrane fuel cell and its preparing method
CN1744360A (en) * 2004-09-01 2006-03-08 中国科学院大连化学物理研究所 Composite catalytic layer proton exchange membrane fuel cell electrode and manufacture method thereof
US20070259253A1 (en) * 2006-03-31 2007-11-08 Samsung Sdi Co., Ltd. Electrode for fuel cell, membrane-electrode assembly for fuel cell, and fuel cell system including the same
CN102005582A (en) * 2010-09-28 2011-04-06 中国科学院上海微系统与信息技术研究所 Structure of direct alcohol fuel cell membrane electrode aggregate and preparation method thereof
CN102315457A (en) * 2011-08-03 2012-01-11 哈尔滨工业大学 Passive miniature methanol fuel cell membrane electrode and its preparation method
CN106229533A (en) * 2016-08-24 2016-12-14 上海交通大学 Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof
CN110880604A (en) * 2018-09-05 2020-03-13 广州汽车集团股份有限公司 Proton exchange membrane fuel cell membrane electrode and preparation method thereof
CN111490277A (en) * 2020-04-20 2020-08-04 淄博火炬能源有限责任公司 Membrane electrode of medium-temperature proton exchange membrane fuel cell and preparation method thereof
CN113130951A (en) * 2021-04-02 2021-07-16 上海电气集团股份有限公司 Membrane electrode, preparation method thereof and fuel cell

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1612381A (en) * 2003-10-27 2005-05-04 中国科学院大连化学物理研究所 Membrane electrode structure for proton exchange membrane fuel cell and its preparing method
CN1744360A (en) * 2004-09-01 2006-03-08 中国科学院大连化学物理研究所 Composite catalytic layer proton exchange membrane fuel cell electrode and manufacture method thereof
US20070259253A1 (en) * 2006-03-31 2007-11-08 Samsung Sdi Co., Ltd. Electrode for fuel cell, membrane-electrode assembly for fuel cell, and fuel cell system including the same
CN102005582A (en) * 2010-09-28 2011-04-06 中国科学院上海微系统与信息技术研究所 Structure of direct alcohol fuel cell membrane electrode aggregate and preparation method thereof
CN102315457A (en) * 2011-08-03 2012-01-11 哈尔滨工业大学 Passive miniature methanol fuel cell membrane electrode and its preparation method
CN106229533A (en) * 2016-08-24 2016-12-14 上海交通大学 Compound Multilayer Film Electrode of hydrophilic/hydrophobic and preparation method thereof
CN110880604A (en) * 2018-09-05 2020-03-13 广州汽车集团股份有限公司 Proton exchange membrane fuel cell membrane electrode and preparation method thereof
CN111490277A (en) * 2020-04-20 2020-08-04 淄博火炬能源有限责任公司 Membrane electrode of medium-temperature proton exchange membrane fuel cell and preparation method thereof
CN113130951A (en) * 2021-04-02 2021-07-16 上海电气集团股份有限公司 Membrane electrode, preparation method thereof and fuel cell

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