CN117039011B - Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell - Google Patents
Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell Download PDFInfo
- Publication number
- CN117039011B CN117039011B CN202310940507.4A CN202310940507A CN117039011B CN 117039011 B CN117039011 B CN 117039011B CN 202310940507 A CN202310940507 A CN 202310940507A CN 117039011 B CN117039011 B CN 117039011B
- Authority
- CN
- China
- Prior art keywords
- layer
- microporous layer
- hydrophilic
- preparation
- agent
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 41
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 16
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004917 carbon fiber Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 229910010293 ceramic material Inorganic materials 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 abstract description 15
- 238000009826 distribution Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000006255 coating slurry Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 235000019241 carbon black Nutrition 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000006256 anode slurry Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006257 cathode slurry Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000338 in vitro Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003698 laser cutting Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012806 monitoring device Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000010023 transfer printing Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- H01M4/88—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
- H01M4/8605—Porous electrodes
- H01M4/861—Porous electrodes with a gradient in the porosity
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a composite microporous layer, a preparation method thereof and a proton exchange membrane fuel cell, wherein a hydrophobic microporous layer is firstly prepared on the surface of a catalytic layer so as to reduce the resistance between the diffusion layer and the catalytic layer and increase the drainage; and then preparing a hydrophilic microporous layer on the surface of the hydrophobic microporous layer, and preparing a conductive leveling layer which is beneficial to gas transmission and improves the distribution of gas and water through gradient microporous distribution. Compared with the prior art, the method for preparing the microporous layer by one-step molding by coating slurry on one side of the carbon substrate in the prior art is changed, and the resistance between the diffusion layer and the catalytic layer can be reduced, so that the drainage property is increased; and the preparation method is simple and easy to popularize.
Description
Technical Field
The invention belongs to the technical field of proton exchange membrane fuel cells, relates to a membrane electrode microporous layer of a fuel cell for a vehicle, and in particular relates to a composite microporous layer, a preparation method thereof and a proton exchange membrane fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are power generation devices capable of directly converting chemical energy of fuel into electric energy, and have the characteristics of environmental friendliness, high energy conversion efficiency, long service life and the like, and have been widely applied in various fields. The Membrane Electrode (MEA) is used as a reaction place of the proton exchange membrane fuel cell, directly determines the energy conversion efficiency of the fuel cell, and belongs to a core component of the proton exchange membrane fuel cell. The membrane consists of a Proton Exchange Membrane (PEM), a Catalytic Layer (CL) and a diffusion layer (GDL) from inside to outside. The main stream of membrane electrode preparation at present is a CCM membrane electrode preparation process: and (3) coating the catalyst on a proton exchange membrane, directly preparing the microporous layer on the gas diffusion layer, and finally attaching the microporous layer and the gas diffusion layer.
The Gas Diffusion Layer (GDL) has the functions of reactant gas distribution, water production diversion, electric conduction, support and the like. Reasonable gas diffusion structure is a key influencing factor of heat and mass transfer of proton exchange membrane fuel cells. The gas diffusion layer is typically a bilayer structure including a carbon substrate (or referred to as a substrate layer GDB) and a microporous layer (MPL). Since the microporous layer is usually prepared on the gas diffusion layer, when the microporous layer and the proton exchange membrane coated with the catalytic layer prepared by the CCM process are pressed together, an interface exists between the microporous layer and the catalytic layer, and liquid water is usually retained on the interface to influence gas transmission, when the porosity of the carbon substrate is too large, flooding caused by too large water breakthrough pressure can be caused, and if a strong interface effect exists between the carbon substrate and the microporous layer, a large amount of water is accumulated, and a formed liquid water film can influence a gas transmission path.
The current microporous layer preparation method is that one side of a carbon substrate is coated with slurry for one-step forming, and when the process is applied to carbon paper with larger porosity, the drainage performance of the carbon paper is extremely poor. And the excessive temperature during the primary hydrophobic treatment of the carbon substrate can cause the increase of energy consumption, which is unfavorable for environmental protection.
The patent with publication number CN 108075158A published in 5 and 25 in 2018 discloses a preparation method of a CCM membrane electrode of a fuel cell, which provides an optimized transfer printing method for producing the CCM membrane electrode, a transition layer with a component close to a microporous layer is added between a catalytic layer and a transfer printing film, and the problems of water management at the interface of the catalytic layer and the microporous layer, mass transfer caused by the water management and the like can be solved. But the actual use effect is not ideal.
Patent publication number CN 111584887A, 25 in 2020 discloses a "preparation method of a gas diffusion layer for proton exchange membrane fuel cell", which pretreats a carbon substrate by polishing or applying pressure to increase the surface roughness of the carbon substrate, thereby increasing the bonding degree of the microporous layer and the carbon substrate, but the pretreat method damages the pore size structure of the carbon substrate and affects the flatness of the microporous layer, and finally affects the performance of the gas diffusion layer.
Patent publication number CN 112133931A, published in 12/25/2020 discloses a "preparation method of a double microporous layer of a gas diffusion layer of a proton exchange membrane fuel cell", which is to add excessive organic solvent and excessive nano-material cost into the slurry in order to manufacture the double microporous layer, which will seriously affect the pore structure and manufacturing cost of the gas diffusion layer.
Therefore, the prior art is not ideal in improving the flooding effect and reducing the contact resistance, and other problems such as high cost, performance influence and the like are brought.
Disclosure of Invention
The invention aims to provide a composite microporous layer and a preparation method thereof, wherein the composite microporous layer is prepared on the surface of a catalytic layer based on the catalytic layer, so that the resistance between a diffusion layer and the catalytic layer is reduced, and the drainage property is increased; and then preparing a hydrophilic microporous layer on the surface of the hydrophobic microporous layer, and preparing a conductive leveling layer which is beneficial to gas transmission and improves the distribution of gas and water through gradient microporous distribution.
The proton exchange membrane fuel cell provided by the invention comprises the composite microporous layer.
The specific technical scheme of the invention is as follows:
a method of preparing a composite microporous layer comprising the steps of:
1) Preparing a hydrophobic microporous layer on the surface of the catalytic layer;
2) And preparing a hydrophilic microporous layer on the surface of the hydrophobic microporous layer.
The hydrophobic microporous layer in the step 1) is a carbon fiber membrane layer;
the preparation method of the carbon fiber membrane layer comprises the following steps: the polyacrylonitrile fiber is pre-oxidized and carbonized.
The polyacrylonitrile fiber pre-oxidation specifically comprises the following steps: treating polyacrylonitrile fiber in oxidizing atmosphere at 200+/-10 deg.c for 20+/-3 min and at 300+/-10 deg.c for 15+/-2 min to obtain pre-oxidized polyacrylonitrile fiber;
the oxygen volume concentration in the atmosphere is 20-50% in the oxidizing atmosphere environment; the pre-oxidation is generally carried out in an oxidation furnace, and the atmosphere comprises air with the oxygen volume concentration of 20-50%, CO 2,NO2 and the like;
The carbonization is specifically carried out by treating for 4+/-0.2 hours at a high temperature of 800-1200 ℃ under the protection of inert gas to obtain a carbon fiber membrane layer; the inert gas is preferably high-purity nitrogen;
In the step 1), the hydrophobic microporous layer is tightly attached to the catalytic layer, and the porous layer is hot-pressed for 5+/-1 min under the pressure of 130+/-5 ℃ and 0.3+/-0.05 Mpa.
In step 1), the catalytic layers are an anode catalyst layer and a cathode catalyst layer.
The thickness of the hydrophobic microporous layer is 5-40 μm, preferably 8-15 μm;
In the step 2), the method for preparing the hydrophilic microporous layer on the surface of the hydrophobic microporous layer specifically comprises the following steps: coating hydrophilic slurry on the surface of the hydrophobic microporous layer, and performing heat treatment to obtain the porous ceramic.
The hydrophilic slurry includes a hydrophilic agent; the average grain diameter of the hydrophilic agent material is 4nm-200nm.
The hydrophilic agent comprises tin oxide, titanium dioxide or hydrophilic carbon black; hydrophilic carbon blacks have a greater concentration of carboxyl groups than typical carbon blacks;
the hydrophilic slurry also comprises a pore-forming agent, wherein the pore-forming agent comprises ammonium bicarbonate, ammonium carbonate or ammonium nitrate;
preferably, the preparation method of the hydrophilic slurry comprises the following steps:
mixing the conductive agent, the hydrophilic agent and the pore-forming agent in a solvent, uniformly mixing by ultrasonic, standing and settling the mixture, and removing supernatant to obtain sediment serving as hydrophilic slurry.
The mass ratio of the conductive agent to the hydrophilic agent to the pore-forming agent is 1.9-2.2:1.8-2.1:1;
The conductive agent is selected from acetylene black or carbon black;
the solvent is a mixed solution of water and ethanol in any proportion;
the dosage ratio of the hydrophilic agent to the solvent is 1:1-8g/mL; preferably 1:1g/mL;
in the step 2), the hydrophilic sizing agent is coated on the surface of the hydrophobic microporous layer, and the hydrophilic sizing agent is specifically: and coating the hydrophilic slurry on the surface of the hydrophobic microporous layer by using a scraper, and performing heat treatment after drying.
In step 2), the thickness of the hydrophilic microporous layer is 0.23-0.48 mm, preferably 0.3mm;
hydrophilic agent is adopted as hydrophilic carbon black and carbon black is adopted as conductive agent, the loading capacity of the carbon material on the surface of the catalytic layer is 0.9-2.8 mg/cm 2, preferably 1.6mg/cm 2;
In the step 2), the heat treatment is carried out in a nitrogen atmosphere of a tube furnace to obtain a carbon powder layer, wherein the heat treatment temperature is 200-400 ℃ and the time is 30-120 min.
The invention uses the composite microporous layer material to directly coat the catalytic layer, optimizes the process sequence and method of the microporous layer, namely, the invention firstly carries out hydrophobization treatment and then hydrophilization treatment based on the catalytic layer, and changes the method of preparing the microporous layer by one-step molding by coating slurry on one side of a carbon substrate in the prior art. When the microporous layer is prepared, the microporous layer on one side close to the catalytic layer is subjected to hydrophobization treatment so as to reduce the resistance between the diffusion layer and the catalytic layer and increase the drainage; and carrying out hydrophilization treatment on the microporous layer far away from one side of the catalytic layer, and preparing a conductive and gas-transmission-beneficial smoothening layer by gradient micropore distribution (gradient from small to large in pore size distribution from the center to the outside), so as to reduce the resistance between the diffusion layer and the catalytic layer and improve the distribution of gas and water.
The invention provides a composite microporous layer, which is prepared by adopting the preparation method.
The proton exchange membrane fuel cell provided by the invention comprises the composite microporous layer.
The inventor analyzes that the microporous layer is directly prepared on the gas diffusion layer and is mutually attached with the proton membrane coated with the catalyst, so that contact resistance exists, and the energy conversion efficiency is reduced; the CCM type MEA is easy to generate catalyst CO poisoning and 'flooding' phenomenon in the operation process of the fuel cell, and the main reason is that the catalytic layer of the MEA is free of a hydrophobic agent, less in gas channels and larger in gas and water transmission resistance.
The microporous layer in the prior art generally has the problem of unreasonable pore structure, and in order to solve the technical problems, the invention provides a composite microporous layer and a preparation method thereof, which are double microporous layer preparation technologies. Compared with the prior art, the method has the advantages that the carbon fiber film layer with the pore size and the pore size between the gas diffusion layers is constructed on the side close to the catalytic layer, the carbon fiber film layer has the hydrophobic characteristic and higher porosity, and the micro-scale pores and the nano-scale pores exist on the surface close to the catalytic layer, so that the air permeability is ensured, and meanwhile, the surface flatness is high, the contact resistance between the microporous layer and the catalytic layer is reduced, the water retention is reduced, and the flooding risk is reduced; coating a carbon powder layer on the carbon fiber film layer to form a microporous layer far away from the catalytic layer, and utilizing pore-forming agent and hydrophilic agent to gradually increase gradient pores so as to facilitate water to be discharged outwards; the preparation method is simple and easy to popularize.
Drawings
FIG. 1 is a schematic structural view of a composite microporous layer according to the present invention;
In the figure: 1-proton membrane, 21-anode catalytic layer, 22-cathode catalytic layer, 3-hydrophobic microporous layer and 4-hydrophilic microporous layer.
FIG. 2 is test data of polarization curves of samples of inventive example 1 and comparative example 1;
FIG. 3 is test data of impedance curves of samples of inventive example 1 and comparative example 1.
Detailed Description
Example 1
A method of preparing a composite microporous layer comprising the steps of:
1) Treating polyacrylonitrile fibers obtained by electrostatic spinning in an air atmosphere with the oxygen volume concentration of 35 percent at the temperature of 200 ℃ for 20 minutes, and then treating the polyacrylonitrile fibers in the temperature of 300 ℃ for 15 minutes to obtain pre-oxidized polyacrylonitrile fibers, and then treating the pre-oxidized polyacrylonitrile fibers at the high temperature of 1000 ℃ for 4 hours under the protection of high-purity nitrogen to obtain carbon fiber films; the obtained carbon fiber film is respectively clung to the anode catalytic layer and the anode catalytic layer, and is hot-pressed for 5 minutes under the pressure of 0.3Mpa at 130 ℃ to obtain the hydrophobic microporous layer with the thickness of 11 mu m.
2) Water and ethanol according to the volume ratio of 1:1 as a solvent, mixing the conductive agent carbon black, titanium dioxide and ammonium bicarbonate according to the mass ratio of 2:2:1, adding the mixture into the solvent, wherein the dosage ratio of the titanium dioxide to the solvent is 1:1g/mL, oscillating with ultrasonic waves, uniformly mixing, and standing for sedimentation; after the supernatant is removed, coating the sediment on the surface of the catalytic layer with microporous layer slurry by using a lithium electric scraper, adjusting the thickness of a slurry liquid film by setting the height of the scraper, and drying; the height of the scraper is 0.3mm, and a hydrophilic microporous layer of 0.3mm is obtained, wherein the carbon black loading of the conductive agent is 1.6mg/cm 2; placing the sample in a nitrogen atmosphere of a tube furnace for heat treatment at 400 ℃ for 60 min; and obtaining a carbon powder layer serving as a hydrophilic microporous layer.
Example 2
The proton exchange membrane fuel cell comprises the composite microporous layer, and the preparation method of the proton exchange membrane fuel cell comprises the following steps:
1) Catalyst slurry preparation, coating and drying:
the anode slurry adopts Pt-C catalyst with the mass ratio of 15%, deionized water with the mass ratio of 40%, methanol solvent with the mass ratio of 40% and a poly-in-vitro solution (nafi on solution) with the mass ratio of 5% as adhesives; the cathode slurry uses 20% Pt-C catalyst, 35% deionized water and 35% methanol solvent by weight, 10% poly-isolated solution (nafion solution) as binder. Then the cathode and the anode are respectively prepared and processed, dispersed and stirred, and the sizing agent is uniformly mixed. The dispersing device may be a paddle mixer, a ball mixer, an ultrasonic dispersing device, or the like. The dispersion stirring time is 50-60 min, and the stirring temperature is recommended: stirring rotation speed at 2 ℃): 600-4000 rpm. The prepared anode slurry and cathode slurry are coated and cured on a proton membrane by using a spray gun or other alternative equipment (such as rotary roller screen printing, ink-jet printing, doctor blade coating and the like), a heating conveyor belt and an IR/DC on-line monitoring device, and the anode membrane thickness is as follows: 3-15 mu m; cathode film thickness: 10-30 mu m, feeding speed: 0.1-1 m/min, drying time: about 4 minutes, drying temperature: heating air flow to 30-70 ℃; the heating roller is set at 120-160 ℃ and is tested by XRF, and the cathode platinum carrying capacity is as follows: anode platinum loading of 0.35mg/cm 2: 0.05mg/cm2;
2) Treating polyacrylonitrile fibers obtained by electrostatic spinning in an air atmosphere with the oxygen volume concentration of 35 percent at the temperature of 200 ℃ for 20 minutes, and then treating the polyacrylonitrile fibers in the temperature of 300 ℃ for 15 minutes to obtain pre-oxidized polyacrylonitrile fibers, and then treating the pre-oxidized polyacrylonitrile fibers at the high temperature of 1000 ℃ for 4 hours under the protection of high-purity nitrogen to obtain carbon fiber films; the obtained carbon fiber film is respectively clung to the anode catalytic layer and the anode catalytic layer, and is hot-pressed for 5 minutes under the pressure of 0.3Mpa at 130 ℃ to obtain the hydrophobic microporous layer with the thickness of 11 mu m.
3) Water and ethanol according to the volume ratio of 1:1 as a solvent, mixing the conductive agent carbon black, titanium dioxide and ammonium bicarbonate according to the mass ratio of 2:2:1, adding the mixture into the solvent, wherein the dosage ratio of the titanium dioxide to the solvent is 1:1g/mL, oscillating with ultrasonic waves, uniformly mixing, and standing for sedimentation; after the supernatant is removed, coating the sediment on the surface of the catalytic layer with microporous layer slurry by using a lithium electric scraper, adjusting the thickness of a slurry liquid film by setting the height of the scraper, and drying; the height of the scraper is 0.3mm, and a hydrophilic microporous layer of 0.3mm is obtained, wherein the carbon black loading of the conductive agent is 1.6mg/cm 2; placing the sample in a nitrogen atmosphere of a tube furnace for heat treatment at 400 ℃ for 60 min; and obtaining a carbon powder layer serving as a hydrophilic microporous layer.
4) And (3) laminating: the preparation is completed to obtain CCM (continuous micro porous membrane) of a cathode catalytic layer 22, an anode catalytic layer 21 and a double-layer micro porous layer (a hydrophobic micro porous layer 3 and a hydrophilic micro porous layer 4) which are respectively attached to the surface of the proton membrane 1, a laser cutting machine is used for feeding CCM, PEN frames and diffusion layer carbon substrates, active area cutting is carried out, the cut frames and CCM are placed, sheet materials are aligned and attached to form five layers of MEAs, the sheet material diffusion layer carbon substrates are placed, the cathode and anode diffusion layer carbon substrates are glued, a thermosetting device (a hot press) is placed, seven layers of MEAs are assembled, and air tightness detection and electric property detection are sequentially carried out on the product. The connection is carried out through hot pressing, and the hot pressing temperature is as follows: 100-160 ℃. Contact pressure: 1.000 to 10.000kgf/cm2.
Comparative example 1
A preparation method of a proton exchange membrane fuel cell comprises the following steps:
1) Catalyst slurry preparation, coating and drying:
The anode slurry adopts 15% of Pt-C catalyst, 40% of deionized water and 40% of methanol solvent in mass ratio and 5% of poly-in-vitro solution (nafion solution) in mass ratio as adhesive; the cathode slurry adopts a Pt-C catalyst with the mass ratio of 20 percent, deionized water with the mass ratio of 35 percent, a methanol solvent with the mass ratio of 35 percent and a 10 percent in-vitro polymer solution (nafion solution) as binders. Then the cathode and the anode are respectively prepared and processed, dispersed and stirred, and the sizing agent is uniformly mixed. The dispersing device may be a paddle mixer, a ball mixer, an ultrasonic dispersing device, or the like. The dispersion stirring time is 50-60 min, and the stirring temperature is recommended: stirring rotation speed at 2 ℃): 600-4000 rpm. The prepared anode slurry and cathode slurry are coated and cured on a proton membrane by using a spray gun or other alternative equipment (such as rotary roller screen printing, ink-jet printing, doctor blade coating and the like), a heating conveyor belt and an IR/DC on-line monitoring device, and the anode membrane thickness is as follows: 3-15 mu m; cathode film thickness: 10-30 mu m, feeding speed: 0.1-1 m/min, drying time: about 4 minutes, drying temperature: heating the air flow to about 30-70 ℃; the heated roll was set to about 120-160 ℃ and tested using XRF, cathode platinum loading: anode platinum loading of 0.35mg/cm 2: 0.05mg/cm2;
2) And (3) laminating: and (3) after the preparation, the CCM which is respectively attached to the cathode catalytic layer and the anode catalytic layer on the surface of the proton membrane is obtained, a laser cutting machine is used for feeding the CCM and the PEN frame, carrying out active region cutting, placing the cut frame and the CCM, aligning and attaching the sheets to form five layers of MEAs, placing the sheet and the Gas Diffusion Layer (GDL) with the microporous layer, dispensing the Gas Diffusion Layer (GDL) with the microporous layer on the cathode and the anode, placing the Gas Diffusion Layer (GDL) with the microporous layer into a heat curing device (a hot press), carrying out seven-layer MEA assembly, and sequentially carrying out air tightness detection and electric property detection on the product. The connection is carried out through hot pressing, and the hot pressing temperature is as follows: 100-160 ℃. Contact pressure: 1.000 to 10.000kgf/cm2.
The test data for the polarization curves of the samples of example 1 and comparative example 1 are shown in fig. 2; test data for the sample impedance curves of example 1 and comparative example 1 are shown in fig. 3.
From the polarization graph, it can be seen that example 1 is higher in power density than comparative example 1 at current densities of 0.5 to 1.4A/cm 2, and that example 1 is more prominent at low current densities; from the impedance plot it can be seen that the impedance of example 1 is significantly lower than the sample of comparative example 1. The analysis is due to the fact that example 1 more rapidly transmits water generated on the surface of the catalytic layer from the inner hydrophobic microporous layer to the hydrophilic microporous layer, diffusion of water reduces the resistance, and as the amount of water increases, the power densities of example 1 and comparative example 1 are substantially identical after transition when the water "saturates" when the current density reaches 1.4A/cm 2.
Claims (7)
1. A method of preparing a composite microporous layer, the method comprising the steps of:
1) Preparing a hydrophobic microporous layer on the surface of the catalytic layer;
2) Preparing a hydrophilic microporous layer on the surface of the hydrophobic microporous layer;
In the step 1), the catalytic layers are an anode catalyst layer and a cathode catalyst layer;
in the step 2), the method for preparing the hydrophilic microporous layer on the surface of the hydrophobic microporous layer specifically comprises the following steps: coating hydrophilic slurry on the surface of the hydrophobic microporous layer, and performing heat treatment to obtain the porous ceramic material;
The hydrophilic slurry comprises a hydrophilic agent, wherein the hydrophilic agent comprises tin oxide, titanium dioxide or hydrophilic carbon black;
The preparation method of the hydrophilic slurry comprises the following steps:
mixing a conductive agent, a hydrophilic agent and a pore-forming agent in a solvent, uniformly mixing by ultrasonic, standing and settling the mixture, and removing supernatant to obtain sediment serving as hydrophilic slurry; the mass ratio of the conductive agent to the hydrophilic agent to the pore-forming agent is 1.9-2.2:1.8-2.1:1;
The average grain diameter of the hydrophilic agent material is 4nm-200nm.
2. The method of claim 1, wherein the hydrophobic microporous layer of step 1) is a carbon fiber membrane layer.
3. The preparation method of claim 2, wherein the preparation method of the carbon fiber membrane layer comprises the following steps: pre-oxidizing polyacrylonitrile fiber and carbonizing.
4. A method according to claim 3, wherein the pre-oxidation of the polyacrylonitrile fiber is specifically: and (3) treating the polyacrylonitrile fiber for 20+/-3 minutes at the temperature of 200+/-10 ℃ in an oxidizing atmosphere environment, and then treating for 15+/-2 minutes at the temperature of 300+/-10 ℃ to obtain the pre-oxidized polyacrylonitrile fiber.
5. The method according to claim 3 or 4, wherein in step 1), the hydrophobic microporous layer is adhered to the catalyst layer, and the heat pressing is performed at 130.+ -. 5 ℃ and 0.3.+ -. 0.05MPa for 5.+ -. 1min.
6. A composite microporous layer made by the method of any one of claims 1-5.
7. A proton exchange membrane fuel cell comprising the composite microporous layer of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940507.4A CN117039011B (en) | 2023-07-28 | 2023-07-28 | Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310940507.4A CN117039011B (en) | 2023-07-28 | 2023-07-28 | Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117039011A CN117039011A (en) | 2023-11-10 |
| CN117039011B true CN117039011B (en) | 2024-06-07 |
Family
ID=88629071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310940507.4A Active CN117039011B (en) | 2023-07-28 | 2023-07-28 | Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117039011B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011149442A1 (en) * | 2010-05-24 | 2011-12-01 | Utc Power Corporation | Fuel cell having a hydrophilic nanoporous region |
| CN103956505A (en) * | 2014-04-16 | 2014-07-30 | 武汉理工新能源有限公司 | Gas diffusion layer with water retaining property for fuel cell, preparation method of gas diffusion layer, membrane electrode assembly and application |
| CN212303709U (en) * | 2020-07-23 | 2021-01-05 | 内蒙古工业大学 | Novel high-temperature fuel cell monocell structure |
| CN114824298A (en) * | 2022-04-12 | 2022-07-29 | 安徽枡水新能源科技有限公司 | Preparation method of microporous layer in gas diffusion layer of hydrogen fuel cell |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4691914B2 (en) * | 2004-06-21 | 2011-06-01 | 日産自動車株式会社 | Gas diffusion electrode and solid polymer electrolyte fuel cell |
| GB201914335D0 (en) * | 2019-10-04 | 2019-11-20 | Johnson Matthey Fuel Cells Ltd | Membrane electrode assembly |
-
2023
- 2023-07-28 CN CN202310940507.4A patent/CN117039011B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011149442A1 (en) * | 2010-05-24 | 2011-12-01 | Utc Power Corporation | Fuel cell having a hydrophilic nanoporous region |
| CN103956505A (en) * | 2014-04-16 | 2014-07-30 | 武汉理工新能源有限公司 | Gas diffusion layer with water retaining property for fuel cell, preparation method of gas diffusion layer, membrane electrode assembly and application |
| CN212303709U (en) * | 2020-07-23 | 2021-01-05 | 内蒙古工业大学 | Novel high-temperature fuel cell monocell structure |
| CN114824298A (en) * | 2022-04-12 | 2022-07-29 | 安徽枡水新能源科技有限公司 | Preparation method of microporous layer in gas diffusion layer of hydrogen fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| 微型DMFC用新型双催化层膜电极的制备;索春光;张文斌;王华;文斯;;江苏大学学报(自然科学版);20131104(06);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117039011A (en) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113394409B (en) | Hydrogen fuel cell gas diffusion layer with double-microporous-layer structure and preparation method thereof | |
| EP1704609B1 (en) | Gas diffusion electrodes and membrane electrode assemblies for proton exchange membrane fuel cells | |
| CN101557001B (en) | Fuel cell film electrode and preparation method thereof | |
| CN110190295B (en) | Low-pressure low-humidity fuel cell gas diffusion layer, fuel cell and preparation method | |
| KR101164874B1 (en) | Method for manufacturing mea using low temperature transfer methods, mea manufactured using the method and fuel cell using the mea | |
| CN101355166A (en) | Method for preparing membrane electrode of fuel batter with proton exchange film | |
| CN111129555A (en) | Carbon paper material for high-toughness high-conductivity proton exchange membrane battery | |
| CN114430050A (en) | Gas diffusion layer for high-performance hydrogen fuel cell and preparation method thereof | |
| CN114267845A (en) | Fuel cell gas diffusion layer and preparation method thereof | |
| CN117039011B (en) | Composite microporous layer, preparation method thereof and proton exchange membrane fuel cell | |
| CN110247065B (en) | Low-cost continuous industrial production process of gas diffusion layer of fuel cell | |
| CN116581321B (en) | Fuel cell gas diffusion layer with gradient hole distribution and preparation method thereof | |
| CN110783593B (en) | Fuel cell gas diffusion layer and preparation method thereof | |
| JP2004335252A (en) | Electrode catalyst for fuel cell, and its manufacturing method | |
| CN112970138A (en) | Gas diffusion electrode, method for producing gas diffusion electrode, membrane electrode assembly, and fuel cell | |
| CN112259747B (en) | Fuel cell membrane electrode assembly formed by growing whiskers and preparation method | |
| JP2008311181A (en) | Membrane electrode assembly, its manufacturing method, and fuel cell using the membrane electrode assembly | |
| CN113764685A (en) | Preparation method of gas diffusion layer | |
| CN114050276A (en) | Fuel cell membrane electrode, preparation method thereof and fuel cell | |
| JP5322213B2 (en) | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell | |
| CN112952165A (en) | Direct methanol fuel cell membrane electrode and preparation and application thereof | |
| JP4519246B2 (en) | Method for producing solid polymer fuel cell | |
| CN113948719B (en) | Gas diffusion layer with high air permeability and preparation method thereof | |
| CN212366003U (en) | Low-pressure low-humidity fuel cell gas diffusion layer and fuel cell | |
| CN117374313B (en) | Gas diffusion layer of proton exchange membrane fuel cell and preparation method and application 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 |