CN114520339B - CCM for fuel cell and preparation method thereof - Google Patents
CCM for fuel cell and preparation method thereof Download PDFInfo
- Publication number
- CN114520339B CN114520339B CN202210093007.7A CN202210093007A CN114520339B CN 114520339 B CN114520339 B CN 114520339B CN 202210093007 A CN202210093007 A CN 202210093007A CN 114520339 B CN114520339 B CN 114520339B
- Authority
- CN
- China
- Prior art keywords
- layer
- platinum
- hydrophobic
- ionic polymer
- ccm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 63
- 239000012528 membrane Substances 0.000 claims abstract description 51
- 230000003197 catalytic effect Effects 0.000 claims abstract description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 124
- 239000003054 catalyst Substances 0.000 claims description 92
- 229910052697 platinum Inorganic materials 0.000 claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- 229920000831 ionic polymer Polymers 0.000 claims description 52
- 239000002002 slurry Substances 0.000 claims description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 43
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000554 ionomer Polymers 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 230000002940 repellent Effects 0.000 claims 1
- 239000005871 repellent Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 45
- 210000004027 cell Anatomy 0.000 description 30
- 238000011068 loading method Methods 0.000 description 23
- 238000005303 weighing Methods 0.000 description 21
- 229910000510 noble metal Inorganic materials 0.000 description 19
- 238000002604 ultrasonography Methods 0.000 description 15
- 238000005507 spraying Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 10
- 239000010931 gold Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- BDOYPFKKGPWJBQ-UHFFFAOYSA-N [N].S=O Chemical class [N].S=O BDOYPFKKGPWJBQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 201000000760 cerebral cavernous malformation Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- H01M4/90—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a CCM for a fuel cell and a preparation method thereof, and relates to the field of fuel cells. A CCM for fuel cell comprises a proton exchange membrane and catalytic layers positioned at two sides of the proton exchange membrane, wherein the catalytic layers are divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane outwards. The invention provides the CCM for the fuel cell, which has good drainage effect and good degradation and loss resistance durability, and the preparation method is simple to operate and is suitable for batch production and laboratory operation.
Description
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, and unlike a conventional Cell, the Fuel Cell directly converts chemical energy into electric energy in an electrochemical manner. The method is free from the heat engine process, is not limited by the Carnot cycle, has high energy conversion efficiency (40% -60%), is environment-friendly, and hardly discharges nitrogen-sulfur oxides. The fuel cell has been a hot spot for research in various countries in the world due to its excellent performance, and has been playing a great role in power generation, mobile power supply, and vehicle power supply. The fuel cell automobile is increasingly studied, but the commercialization of the fuel cell automobile still has the technical bottleneck problem, a large amount of water generated during the operation of the fuel cell easily enters the electrode holes, the partial flooding caused by the difficulty in draining the water covered on the surface of the catalytic layer prevents the effective contact of the reaction gas and the catalyst, and thus the electrode performance is reduced. The noble metal catalyst of the catalytic 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 component, which is prepared by coating fuel cell catalysts on two sides of a proton exchange membrane, and is called CCM (catalyst coated membrane) for short. Compared with the membrane electrode MEA (membrane electrode assembly) prepared by coating the catalyst on the surface of a gas diffusion layer (namely carbon paper or carbon cloth), the CCM has the following advantages: 1) The catalyst layer is ultra-thin, and the catalytic efficiency of the catalyst is greatly improved, so that the loading capacity of the Pt noble metal catalyst is reduced (generally can be reduced to below 0.4-0.6mg/cm 2); 2) The proton exchange membrane can be ultrathin, the surface conductivity of the membrane is improved, and the dosage of the membrane is reduced; 3) Short activation time of the battery, quick electrochemical response, etc. Thus, CCM technology is considered to be the second revolution in fuel cell membrane electrode technology.
Patent application CN102325602B discloses a Catalyst Coated Membrane (CCM) and a catalyst membrane/catalyst layer for alkaline membrane fuel cells and a method for preparing the same, a fuel cell cathode catalyst layer based on an unsupported metal particle layer having advantages of inherent stability over a catalyst layer based on carbon supported metal particles. An alkaline membrane fuel cell designed using a silver cathode catalyst includes a catalytic layer including silver metal nano-particles and an anionic conductive ionomer. The silver metal nano-particles are mixed with the ionomer solution to form a catalyst ink which is applied to the alkaline membrane to form an ultra-thin cathode catalytic 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 support layer has higher mechanical strength, and can be used as a current collecting substrate and a diffusion layer frame substrate; the carbon nano tube and the carbon fiber are mixed, the carbon fiber is used as a base frame, the carbon nano tube is used as a filler of the frame, the requirement of high air permeability of the gas diffusion layer is met, and the carbon nano tube has high mechanical strength; the microporous layer can fill the pores with different sizes of the diffusion layer, and can also slow down the uneven phenomenon of the diffusion layer, thereby realizing redistribution of water and reaction gas in the flow field and the catalytic layer, increasing the conductivity and prolonging the service life of the battery.
Therefore, CCMs for fuel cells having excellent durability against degradation loss have become a new research direction.
Disclosure of Invention
The invention aims to provide a CCM for a fuel cell with good drainage effect and good degradation and loss resistance durability and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows: a CCM for fuel cell comprises a proton exchange membrane and catalytic layers adhered to two 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 hydrophilic-hydrophobic gradient structure of the catalytic layer is beneficial to drainage and airflow distribution, and the low-platinum multi-carbon catalyst on two sides of the catalytic layer is degradation-resistant and loss-resistant.
The invention provides a CCM for a fuel cell, which comprises a proton exchange membrane and catalytic layers positioned at two sides of the proton exchange membrane, wherein the catalytic layers are outwards divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane;
wherein the hydrophilic layer comprises a platinum carbon catalyst a, an ionic polymer and a hydrophilic agent, and the mass ratio of carbon to the ionic polymer to the hydrophilic agent in the platinum carbon catalyst a is 1:0.1-10:0.1-10;
The first hydrophobic layer comprises a platinum carbon catalyst b, an ionic polymer and a hydrophobic agent, wherein the mass ratio of carbon to the ionic polymer to 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, wherein the mass ratio of carbon to the ionic polymer to the hydrophobic agent in the platinum carbon catalyst c is 1:0.1-10:0.1-10.
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 solution of threo D83.
Preferably, the hydrophobizing agent is polytetrafluoroethylene solution.
The structure diagram of the CCM is shown in fig. 4, wherein the hydrophilic layer contains hydrophilic agent to facilitate the transfer of the water generated near the proton exchange membrane side in the hydrophilic layer, and when the water in the hydrophilic layer is saturated, the water is transferred to the first hydrophobic layer and the hydrophilic layer, the first hydrophobic layer contains hydrophobic solvent in the hydrophilic layer, and the water can be rapidly and smoothly discharged out of 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, the graphitization treatment specific surface area is low, corrosion, oxidation and attenuation can be prevented, the aggregation and loss of noble metal platinum can be reduced when the oxidation is attenuated due to the low platinum content, and the first hydrophobic layer with high platinum content and high specific surface area and high performance is protected more durably, so that 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 with an ionic polymer, and adding a hydrophobic agent to obtain a first hydrophobic layer slurry;
(3) Mixing a platinum carbon catalyst c with an ionic polymer, and adding a hydrophobic agent to obtain second hydrophobic layer slurry;
(4) Compounding the three slurries on two sides of a proton exchange membrane, wherein the compounding sequence is that one side of the proton exchange membrane is outwards provided with a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer in sequence; thus, a CCM for a fuel cell was obtained.
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 and 4 μm respectively. This thickness ratio works best, with greater 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 step (3) was TANAKA brand EC10VA20E and the platinum mass content was 20%.
Preferably, the ionic polymer is dupont D520.
Preferably, the hydrophilic agent is a threo D83 solution, and the hydrophobic agent is a polytetrafluoroethylene solution.
Specifically, in the step (1), the mass ratio of the platinum-carbon catalyst a to the ionic polymer to the hydrophilic agent is 1:0.1-10:0.1-10;
In the step (2), the mass ratio of the carbon to the ionic polymer to the hydrophobe in the platinum carbon catalyst b is 1:0.1-10:0.5-10;
in the step (3), the mass ratio of the carbon to the ionic polymer to the hydrophobe in the platinum carbon catalyst c is 1:0.1-10:0.1-10.
The beneficial effects are that:
(1) The invention provides a CCM for a fuel cell, which has good drainage effect and good degradation and loss resistance durability. The catalytic 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 hydrophilic layer is arranged on the side, close to the proton membrane, of the catalytic layer, so that a certain amount of moisture can be kept, the proton membrane is kept moist, the proton conductivity is improved, the impedance is reduced, the catalytic layer is suitable for a dry environment, and good performance output is kept. The hydrophobic layer is arranged on the outer side of the catalytic layer, so that water generated in the working process can be well discharged, the gas mass transfer effect is improved, and the electrical property is improved.
(4) The preparation method of the patent is simple to operate, can be applied to conventional preparation processes, does not need special processes, and is suitable for batch production and laboratory operation.
Drawings
FIG. 1 is a graph showing the voltage change under the battery life test in comparative examples 1 and 2; wherein a is a voltage change graph under the battery life test in comparative example 1; wherein B is a voltage change graph under the battery life test in comparative example 2.
FIG. 2 is a graph of voltage change under battery life test in examples 1 and 2; wherein a is a voltage variation graph under the battery life test in example 1; wherein B is a voltage change graph under the battery life test in example 2.
FIG. 3 is a graph of voltage change under battery life test in examples 3 and 4; wherein a is a voltage variation graph under the battery life test in example 3; wherein B is a voltage change graph under the battery life test in example 4.
FIG. 4 is a CCM block diagram; wherein 1 represents a proton exchange membrane; 2 represents 20% platinum content catalyst particles; 3 represents an ionomer containing a hydrophilic agent; 4 represents an ionomer containing a hydrophobizing 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; 9 represents a hydrophilic layer.
Detailed Description
Example 1
(1) Hydrophilic layer slurry preparation:
1) Weighing 20% of platinum content, stirring and mixing TEC10EA20E of graphitized high-durability noble metal catalyst TANAKA brand (noble metal group in the field) with a d520 ionomer solution of DuPont with the mass percentage of 5%, and counting carbon in TEC10EA20E according to mass ratio: ionic polymer=1:1, stirring time 30min;
2) Then adding a hydrophilic solvent of sunwav D83 solution (brand is solvay, model is D83-24B) with the mass percentage of 8%, and counting carbon in TEC10EA20E by mass ratio: hydrophilic agent=1:2, stirring for 20min;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:1, and stirring for 30min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:2;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(3) Preparing a second hydrophobic layer slurry:
1) Weighing 20% of platinum content, mixing and stirring TEC10VA20E of a high-surface-area noble metal catalyst TANAKA brand with d520 ionic polymer solution of DuPont with the mass percentage of 5%, wherein the carbon/ionic polymer in TEC10VA20E is=1:1 in terms of mass ratio, and stirring for 20min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10VA20E to the hydrophobizing agent solution = 1:0.8;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(4) Preparing a catalytic layer:
The uniformly dispersed cathode and anode catalyst layer slurries are respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form cathode and anode catalyst layers, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the proton exchange membrane side outwards, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurries, 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, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(5) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
Example 2
(1) Hydrophilic layer slurry preparation:
1) Weighing 20% of platinum content, stirring and mixing graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with DuPont d520 ionic polymer solution, wherein the mass ratio of carbon in TEC10EA20E to ionic polymer=1:0.7, and stirring for 20min;
2) Then adding a threw D83 solution with the mass percent of the hydrophilic solvent of 8%, and stirring for 20min according to the mass ratio of carbon to hydrophilic agent=1:2 in TEC10EA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:0.6, and stirring for 30min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:2;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(3) Preparing a second hydrophobic layer slurry:
1) Weighing 20% of platinum content, mixing and stirring TEC10VA20E of a high-surface-area noble metal catalyst TANAKA brand with d520 ionic polymer solution of DuPont with the mass percentage of 5%, wherein the carbon/ionic polymer in TEC10VA20E is=1:1 in terms of mass ratio, and stirring for 20min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon to hydrophobizing agent solution=1:2 in TEC10VA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(4) Preparing a catalytic layer:
The uniformly dispersed cathode and anode catalyst layer slurries are respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form cathode and anode catalyst layers, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the proton exchange membrane side outwards, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurries, 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, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(5) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
Example 3
(1) Hydrophilic layer slurry preparation:
1) Weighing 20% of platinum content, stirring and mixing graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with DuPont d520 ionic polymer solution, wherein the mass ratio of carbon in TEC10EA20E to ionic polymer=1:10, and stirring for 40min;
2) Then adding a threw D83 solution with the mass percent of the hydrophilic solvent of 8%, and stirring for 20min according to the mass ratio of carbon to hydrophilic agent=1:10 in TEC10EA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:10, and stirring for 40min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 40min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:10;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(3) Preparing a second hydrophobic layer slurry:
1) Weighing 20% of platinum content, mixing and stirring TEC10VA20E of a high-surface-area noble metal catalyst TANAKA brand with d520 ionic polymer solution of DuPont with the mass percentage of 5%, wherein the carbon/ionic polymer in TEC10VA20E is=1:10 in terms of mass ratio, and stirring for 40min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 40min according to the mass ratio of carbon to hydrophobizing agent solution=1:10 in TEC10VA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(4) Preparing a catalytic layer:
The uniformly dispersed cathode and anode catalyst layer slurries are respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form cathode and anode catalyst layers, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the proton exchange membrane side outwards, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurries, 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, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(5) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
Example 4
(1) Hydrophilic layer slurry preparation:
1) Weighing 20% of platinum content, stirring and mixing graphitized high-durability noble metal catalyst TANAKA brand TEC10EA20E with DuPont d520 ionic polymer solution, wherein the mass ratio of carbon in TEC10EA20E to ionic polymer=1:0.1, and stirring for 10min;
2) Then adding a threw D83 solution with the mass percent of the hydrophilic solvent of 8%, and stirring for 10min according to the mass ratio of carbon to hydrophilic agent=1:0.1 in TEC10EA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:0.1, and stirring for 10min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 10min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:0.5;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(3) Preparing a second hydrophobic layer slurry:
1) Weighing 20% of platinum content, mixing and stirring TEC10VA20E of a high-surface-area noble metal catalyst TANAKA brand with d520 ionic polymer solution of DuPont with the mass percentage of 5%, wherein the carbon/ionic polymer in TEC10VA20E is=1:0.1 in terms of mass ratio, and stirring for 10min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10VA20E to hydrophobizing agent solvent = 1:0.1;
3) Then the whole body is homogenized for 10min by ultrasound for standby;
(4) Preparing a catalytic layer:
The uniformly dispersed cathode and anode catalyst layer slurries are respectively and uniformly sprayed on two sides of a proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form cathode and anode catalyst layers, a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer are sequentially arranged on the proton exchange membrane side outwards, the platinum loading capacity of the catalyst layer is controlled by calculating the platinum content of the catalyst layer slurries, 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, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(5) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
Comparative example 1
(1) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:1, and stirring for 30min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:2;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a catalytic layer:
And respectively and uniformly spraying the uniformly dispersed cathode and anode catalytic layer slurry on two sides of the Golgi proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalytic layer, calculating and controlling the platinum loading of the catalytic layer by the platinum content of the catalytic layer slurry, and verifying the platinum loading in the catalytic layer by weighing. The spraying process parameters are as follows: slurry feed flow rate 0.8mL/min, nozzle speed: 120mm/min, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(3) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
Comparative example 2
(1) Hydrophilic layer slurry preparation:
1) Weighing 20% of platinum content, stirring and mixing TEC10EA20E with a graphitized high-durability noble metal catalyst TANAKA brand and a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10EA20E is=1:1, and stirring time is 30min;
2) Then adding a threw D83 solution with the mass percent of the hydrophilic solvent of 8%, and stirring for 20min according to the mass ratio of carbon to hydrophilic agent=1:2 in TEC10EA 20E;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(2) Preparing a first hydrophobic layer slurry:
1) Weighing 50% of platinum content, mixing and stirring TEC10E50E with a high specific surface area noble metal catalyst TANAKA brand with a dupont d520 ionic polymer solution with a mass percentage of 5%, wherein the mass ratio of carbon to ionic polymer in TEC10E50E is=1:1, and stirring for 30min;
2) Then adding PTFE solution (60% by mass) of the hydrophobizing agent solution Japanese gold D210C, and stirring for 20min according to the mass ratio of carbon in TEC10E50E to the hydrophobizing agent solution=1:2;
3) Then the whole body is homogenized for 40min by ultrasound for standby;
(3) Preparing a catalytic layer:
And uniformly spraying the uniformly dispersed cathode and anode catalytic layer slurry on two sides of the proton exchange membrane M765.08 by adopting ultrasonic spraying equipment to form a cathode and anode catalytic layer, wherein the hydrophilic layer is arranged on one side close to the proton exchange membrane, the platinum content of the catalytic layer is calculated and controlled by the platinum content of the catalytic layer slurry, and the platinum content in the catalytic layer is verified by weighing. The spraying process parameters are as follows: slurry feed flow rate 0.8mL/min, nozzle speed: 120mm/min, shower nozzle height: 35mm, drying temperature: 80 ℃. Wherein the anode platinum loading is 0.05mg/cm 2 and the cathode platinum loading is 0.4mg/cm 2.
(4) And (3) heat treatment:
And (3) putting the proton exchange membrane with the catalyst slurry compounded on both sides into a hot press with flatness of 1-5 wires, and treating for 60min under the conditions of 110 ℃ and 5kg/cm 2 to obtain the CCM for the fuel cell.
The attenuation result of the prepared CCM through cyclic voltammetry is as follows:
after 90 hours, the attenuation is 3.11%, 5.26% and 12.65% under the conditions of 300, 800 and 1200 electric density respectively.
The fuel cells prepared in examples 1-4 and comparative examples 1-2 were subjected to cyclic voltammetry with CCM.
The test results after 50 hours for decay at 300, 800, 1200 current densities, respectively, are shown in table 1 and figures 1-3.
TABLE 1
| Sample numbering | 300% Of electric density attenuation | 800% Of electric density attenuation | 1200% Of electric 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, the CCM prepared by the method of the invention has greatly improved life durability.
Claims (4)
1. The CCM for the fuel cell comprises a proton exchange membrane and catalytic layers positioned at two sides of the proton exchange membrane, and is characterized in that the catalytic layers are outwards divided into a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer from one side of the proton exchange membrane;
wherein the hydrophilic layer comprises a platinum carbon catalyst a, an ionic polymer and a hydrophilic agent, and the mass ratio of carbon to the ionic polymer to the hydrophilic agent in the platinum carbon catalyst a is 1:0.1-10:0.1-10;
The first hydrophobic layer comprises a platinum carbon catalyst b, an ionic polymer and a hydrophobic agent, wherein the mass ratio of carbon to the ionic polymer to 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, wherein the mass ratio of carbon to the ionic polymer to the hydrophobic agent in the platinum carbon catalyst c is 1:0.1-10:0.1-10;
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%;
the preparation method of the CCM for the fuel cell 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 with an ionic polymer, and adding a hydrophobic agent to obtain a first hydrophobic layer slurry;
(3) Mixing a platinum carbon catalyst c with an ionic polymer, and adding a hydrophobic agent to obtain second hydrophobic layer slurry;
(4) Compounding the three slurries on two sides of a proton exchange membrane, wherein the compounding sequence is that one side of the proton exchange membrane is outwards provided with a hydrophilic layer, a first hydrophobic layer and a second hydrophobic layer in sequence; thus, a CCM for a fuel cell was obtained.
2. The CCM for a fuel cell of claim 1, wherein the ionomer is dupont D520.
3. The CCM for a fuel cell according to claim 1, wherein the hydrophilic agent is a suwei D83 solution.
4. The CCM for a fuel cell according to claim 1, wherein the water repellent agent is a polytetrafluoroethylene solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210093007.7A CN114520339B (en) | 2022-01-26 | 2022-01-26 | CCM for fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210093007.7A CN114520339B (en) | 2022-01-26 | 2022-01-26 | CCM for fuel cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114520339A CN114520339A (en) | 2022-05-20 |
| CN114520339B true CN114520339B (en) | 2024-06-14 |
Family
ID=81597087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210093007.7A Active CN114520339B (en) | 2022-01-26 | 2022-01-26 | CCM for fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114520339B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100521313C (en) * | 2003-10-27 | 2009-07-29 | 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 |
| KR20070098136A (en) * | 2006-03-31 | 2007-10-05 | 삼성에스디아이 주식회사 | Membrane-electrode assembly for fuel cell and fuel cell system comprising same |
| CN102315457B (en) * | 2011-08-03 | 2013-12-04 | 哈尔滨工业大学 | Passive miniature methanol fuel cell membrane electrode and its preparation method |
| 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 |
| CN215496795U (en) * | 2021-03-08 | 2022-01-11 | 上海智能制造功能平台有限公司 | Multi-level fuel cell catalyst layer structure |
-
2022
- 2022-01-26 CN CN202210093007.7A patent/CN114520339B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114520339A (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4144686B2 (en) | Method for producing polymer electrolyte fuel cell | |
| CN101557001B (en) | Fuel cell film electrode and preparation method thereof | |
| US20090047559A1 (en) | Fuel cell electrode catalyst with improved noble metal utilization efficiency, method for manufacturing the same, and solid polymer fuel cell comprising the same | |
| CN109524674B (en) | Method for improving performance of cathode catalyst layer of membrane electrode of fuel cell | |
| CN101000967A (en) | Membrane electrode of protone exchange membrane fuel cell and preparation method thereof | |
| CN107634229B (en) | Membrane electrode for fuel cell stack | |
| CN111370717A (en) | Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell | |
| CN112382767B (en) | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer | |
| CN111261878B (en) | Catalyst slurry containing aqueous gel, catalyst layer and fuel cell electrode produced therefrom | |
| CN111584880B (en) | Low-platinum proton exchange membrane fuel cell membrane electrode and preparation method thereof | |
| CN103280583A (en) | Method for preparing catalytic layer structure of proton exchange membrane fuel cell | |
| US7094492B2 (en) | Electrode for polymer electrolyte fuel cell | |
| JP5297786B2 (en) | Anode catalyst layer of polymer electrolyte fuel cell | |
| JP2003109606A (en) | High molecular electrolyte fuel cell and method of manufacturing the same | |
| JP6571961B2 (en) | ELECTRODE FOR FUEL CELL, MEMBRANE ELECTRODE COMPLEX FOR FUEL CELL, AND FUEL CELL | |
| CN103779582A (en) | Method for preparing fuel cell membrane electrode | |
| CN103367768A (en) | Method for preparing double-catalyst-layer structure of proton exchange membrane fuel cell | |
| CN103326032B (en) | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell | |
| KR100645832B1 (en) | Membrane electrode assembly for pemfc, method for preparing the same, and fuel cell using the same | |
| CN114520339B (en) | CCM for fuel cell and preparation method thereof | |
| CN101771150B (en) | Fuel cell membrane electrode with renewable function and preparation method thereof | |
| CN101783409B (en) | Preparation method of membrane electrode with negative pole being carbon-carried transition metal chelate catalytic agent | |
| JP5326585B2 (en) | Method for producing metal catalyst-supported carbon powder | |
| RU2563029C2 (en) | Method of preparing membrane-electrode units | |
| CN114566653B (en) | Non-uniform catalyst layer, membrane electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |