CN116581308B - Dry membrane electrode preparation method of membrane fuel cell - Google Patents
Dry membrane electrode preparation method of membrane fuel cell Download PDFInfo
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- CN116581308B CN116581308B CN202310851272.1A CN202310851272A CN116581308B CN 116581308 B CN116581308 B CN 116581308B CN 202310851272 A CN202310851272 A CN 202310851272A CN 116581308 B CN116581308 B CN 116581308B
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- 239000000446 fuel Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 229920000557 Nafion® Polymers 0.000 claims abstract description 47
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000009987 spinning Methods 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 150000003460 sulfonic acids Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 16
- 239000012046 mixed solvent Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 7
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000007590 electrostatic spraying Methods 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 101100248253 Arabidopsis thaliana RH40 gene Proteins 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- YOMFVLRTMZWACQ-UHFFFAOYSA-N ethyltrimethylammonium Chemical compound CC[N+](C)(C)C YOMFVLRTMZWACQ-UHFFFAOYSA-N 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/886—Powder spraying, e.g. wet or dry powder spraying, plasma spraying
-
- 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
- H01M4/8864—Extrusion
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The application discloses a dry membrane electrode preparation method of a membrane fuel cell, which comprises the following steps: s1, mixing Nafion film solution, high molecular polymer and mixed solvent according to a proportion, and adopting an electrostatic spinning technology to obtain Nafion fibers; s2, uniformly mixing the soluble powder, the nafion fiber and the catalyst powder; and S3, dispersing the mixture obtained in the step S2 on the surface of the proton exchange membrane, and removing soluble powder in the dry membrane electrode after hot pressing or electrostatic powder spraying to form pores to obtain the dry membrane electrode. The fiber prepared by electrostatic spinning is mixed with the catalyst powder and is directly dispersed on the membrane or the gas diffusion layer to prepare the membrane electrode, the fiber plays a role of bonding the catalyst, the problems that the solvent is easy to cause swelling of the membrane and damage of the membrane are avoided, the production process is simple, the cost is lower, the catalyst activity is higher, and the membrane electrode performance is better.
Description
Technical Field
The application relates to the technical field of fuel cells, in particular to a dry membrane electrode preparation method of a membrane fuel cell.
Background
The membrane electrode of the fuel cell provides a three-phase interface for reaction and is a key part of the membrane fuel cell. The processing technology of the electrode sheet film in the prior art can be classified into a wet process and a dry process according to whether a solvent is used.
The existing wet process requires that the carbon-supported catalyst is added with a solvent (typically alcohols), a binder, etc. to prepare an ink, and then the catalyst is solidified on the membrane or the gas diffusion layer by evaporating the solvent. The method needs a solvent, the catalyst is easy to poison in the process of preparing the ink, and the solvent is easy to cause swelling of the membrane and damage the membrane in the process of preparing the membrane electrode. In addition, the addition of solvent and evaporation of solvent results in longer production times and increased costs.
In the existing dry process, active materials, conductive materials, binders and the like are formed into mixed powder, the mixed powder is extruded and rolled to form a continuous self-supporting dry coating, and the coating is pressed with a current collector to form an electrode plate. However, in order to make the pole piece film thin and surface adhesive, the compaction density is increased, so that the pole piece film is brittle, has small pores and reduces the catalytic activity.
Therefore, there is a need for improvements in the dry membrane electrode preparation of the prior art to address the above-described problems.
Disclosure of Invention
The application overcomes the defects of the prior art and provides a dry membrane electrode preparation method of a membrane fuel cell.
In order to achieve the above purpose, the application adopts the following technical scheme: a method for preparing a dry membrane electrode of a membrane fuel cell, comprising the steps of:
s1, mixing Nafion film solution, high molecular polymer and mixed solvent according to a proportion, and adopting an electrostatic spinning technology to obtain Nafion fibers;
s2, uniformly mixing the soluble powder, the nafion fiber and the catalyst powder;
and S3, dispersing the mixture obtained in the step S2 on the surface of the proton exchange membrane, and removing soluble powder in the dry membrane electrode after hot pressing or electrostatic powder spraying to form pores to obtain the dry membrane electrode.
In a preferred embodiment of the application, the mass ratio of the Nafion film solution to the high molecular polymer to the mixed solvent is 4-10: 0.5 to 1.5:1.
in a preferred embodiment of the application, the mass ratio of the nanofiber to the catalyst powder is 1:0.5 to 5.
In a preferred embodiment of the application, the nafion fiber diameter is 10nm to 1um.
In a preferred embodiment of the application, the mass ratio of the soluble powder to the catalyst powder is 0.1-1: 1.
in a preferred embodiment of the present application, the high molecular polymer is formed by one or more of the following materials: polyvinylpyrrolidone, polyethylene oxide, perfluorinated sulfonic acid resin and polysulfone.
In a preferred embodiment of the application, the catalyst powder is a carbon-based nano platinum, carbon-based nano platinum cobalt alloy, or iron-based powder catalyst.
In a preferred embodiment of the present application, the mixed solvent is composed of one or more of the following materials: n, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethyl sulfoxide.
The application solves the defects existing in the background technology, and has the following beneficial effects:
the application provides a dry membrane electrode of a membrane fuel cell, which is prepared by a dry process, and is prepared by mixing fibers prepared by electrostatic spinning with catalyst powder and directly dispersing the fibers on a membrane or a gas diffusion layer, wherein the fibers play a role of bonding the catalyst, ink is not required to be prepared and solvent is not required to be evaporated, so that the problems of membrane swelling and membrane damage caused by the solvent are avoided, the whole production process is simple, the cost is lower, the catalyst activity is higher, and the membrane electrode performance is better. The membrane electrode prepared by the dry method has no solvent, reduces the poisoning effect of the solvent on the catalyst, reduces the production cost, and is easy for mass production of the membrane electrode.
According to the application, nafion fibers prepared by electrostatic spinning are directly and uniformly mixed with catalyst powder and coated on the surface of a proton exchange membrane, and during the hot pressing process, the nafion fibers wrap the catalyst powder and simultaneously fill the pores of the catalyst powder, so that adhesion to the catalyst is formed, and the phenomenon of powder falling is avoided; meanwhile, nafion fiber is used as an adhesive, so that the problems of catalyst poisoning and the like caused by excessive coverage of a catalyst by a CCM membrane electrode adhesive are avoided, and the performance and the service life of the membrane electrode are improved.
According to the application, the soluble powder nafion fiber and the catalyst powder are uniformly mixed, and after hot pressing, the soluble powder is evaporated or dissolved, so that pores are formed between the catalyst powder and the nafion fiber, the specific surface area inside the catalytic layer on the surface of the thin pole piece film is ensured to be increased, the reaction is facilitated, and the output performance of the battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art;
FIG. 1 is a schematic illustration of a preferred embodiment of the present application wherein nafion fibers are mixed directly with catalyst powder;
fig. 2 is a graph showing the comparison of the performance of the dry electrode of example 1 and example 2 of the present application and the wet membrane electrode of the prior art.
In the figure: 1. nafion fibers; 2. catalyst powder.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways than those described herein, and therefore the scope of the present application is not limited to the specific embodiments disclosed below.
In the description of the present application, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art in a specific case.
The application provides a dry membrane electrode of a membrane fuel cell, which is prepared by a dry process, and is prepared by mixing fibers prepared by electrostatic spinning with catalyst powder 2 and directly dispersing the fibers on a membrane or a gas diffusion layer, wherein the fibers play a role of bonding the catalyst, ink is not required to be prepared and solvent is not required to be evaporated, the problems that the solvent is easy to cause swelling of the membrane and damage of the membrane are avoided, the whole production process is simple, the cost is lower, the catalyst activity is higher, and the membrane electrode performance is better. The membrane electrode prepared by the dry method has no solvent, reduces the poisoning effect of the solvent on the catalyst, reduces the production cost, and is easy for mass production of the membrane electrode.
As shown in fig. 1, a dry membrane electrode preparation method of a membrane fuel cell according to the present application is shown, comprising the steps of:
s1, mixing Nafion film solution, high molecular polymer and mixed solvent according to a proportion, and adopting an electrostatic spinning technology to obtain Nafion fibers;
s2, uniformly mixing the soluble powder, the nafion fiber 1 and the catalyst powder 2;
and S3, dispersing the mixture obtained in the step S2 on the surface of the proton exchange membrane, and removing soluble powder in the dry membrane electrode after hot pressing or electrostatic powder spraying to form pores to obtain the dry membrane electrode.
The high molecular polymer in the application is formed by one or more of the following substances: polyacrylic acid, polyacrylonitrile, polymethylpyrrolidone, and polyethylene oxide. Among them, polymethylpyrrolidone is preferable.
The mixed solvent is composed of one or more of the following substances: n, N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone and dimethyl sulfoxide. Among them, N-dimethylformamide is preferable.
The Nafion membrane solution is a perfluorosulfonic acid type polymer solution.
Wherein, the mass ratio of the Nafion film solution to the high molecular polymer to the mixed solvent is 4-10: 0.5 to 1.5:1. among them, 5 is preferable: 1:1.
the application mixes Nafion film solution, high molecular polymer and mixed solvent according to proportion at 70 ℃ for 12 h, so that the Nafion film solution, the high molecular polymer and the mixed solvent are fully and uniformly mixed, and stands for defoaming to obtain spinningA liquid; the obtained spinning solution is subjected to conjugate electrostatic spinning to obtain continuous nafion fiber 1; wherein the voltage of the conjugated electrostatic spinning high-voltage power supply is 1-10 kV, and the extrusion speed of the spinning solution is 0.6-1 ml h -1 The ambient temperature is 25+/-3 ℃, and the ambient humidity is 40+/-10%.
In the present application, the diameter of the nafion fiber 1 is 10nm to 1um, and further 50 nm to 100nm. The diameter of the nafion fiber 1 can be controlled by adopting electrostatic spinning parameter adjustment and matching with a drawing process, so that the uniformity of the nafion fiber reaches a specified range.
In the application S2, the nafion fiber 1 and the catalyst powder 2 are fully mixed under the strong stirring action. The catalyst powder 2 is carbon-based nano platinum, carbon-based nano platinum cobalt alloy, iron-based powder catalyst and the like, preferably carbon-based nano platinum catalyst, wherein the platinum content is 20%, and the average particle size is 2.0-3.0nm. The mass ratio of the nanofiber to the catalyst powder 2 is 1:0.5 to 5.
In S3, the powder obtained by fully mixing in S2 is dispersed on the surface of the proton exchange membrane in a coating mode. The manner of dispersion here is not limited to spraying, coating, etc.
The spraying mode can be an electrostatic spraying mode, the electrostatic spraying voltage can be 20-38 kV, and the main air flow rate of the electrostatic spraying can be 5-20 psi.
The hot pressing in the present application S4 may employ a method including: the film is prepared by directly rolling through a horizontal roller press by adjusting a roller gap, or by adopting a repeated folding rolling mode. The hot pressing temperature is 100-170 ℃, the hot pressing time is 5-60 min, and the pressure is 20-60 Mpa. The thickness of the finished membrane electrode is more uniform through hot pressing, and the energy density of the battery is improved.
As shown in fig. 2, the nafion fiber 1 prepared by electrostatic spinning is directly and uniformly mixed with the catalyst powder 2 and coated on the surface of the proton exchange membrane, and in the hot pressing process, the nafion fiber 1 wraps the catalyst powder 2 and is filled between the pores of the catalyst powder 2 at the same time, so that adhesion to the catalyst is formed, and the phenomenon of powder falling is avoided; meanwhile, the nafion fiber 1 is used as an adhesive, so that the problems of catalyst poisoning and the like caused by excessive coverage of a catalyst by a CCM membrane electrode adhesive are avoided, and the performance and the service life of the membrane electrode are improved.
In order to further improve the catalytic activity of the dry membrane electrode, the application uniformly mixes the soluble powder, the nafion fiber 1 and the catalyst powder 2. After hot pressing, the dry membrane electrode is immersed into the dispersion and dried after dissolving the soluble powder. Because the soluble powder can be completely dissolved in the dispersion liquid, along with the dissolution of the soluble powder, pores are formed between the catalyst powder 2 and the nafion fiber 1, and the pores are the dissolution positions of the soluble powder, so that the specific surface area inside the catalytic layer on the surface of the thin pole piece film is ensured to be increased, the reaction is facilitated, and the output performance of the battery is improved.
Among them, soluble powders include, but are not limited to: sugar powder, polyvinyl alcohol powder, and the like. The dispersion is water. The mass ratio of the soluble powder to the catalyst powder 2 is 0.1-1: 1. the soluble powder has a particle size not greater than the catalyst powder. The sugar powder may be a red sugar powder.
The method of removing the soluble powder is not limited to dissolution, evaporation or sublimation.
The soluble powder in the present application may also be an evaporative material, including but not limited to: such as ammonium carbonate, ammonium bicarbonate, ammonium chloride, etc., the evaporating material is heated by a laser beam or electrically heated to evaporate and sublimate the evaporating material.
The Nafion film solution, the polyvinylpyrrolidone and the soluble powder are all conventional raw materials, the Nafion film solution is 5wt% of the Nafion film solution, the molecular weight of the polyvinylpyrrolidone is 8000-12000, the catalyst powder is 40-60 meshes, and the soluble powder is 60-80 meshes.
Example 1
A dry method membrane electrode preparation method of a membrane fuel cell comprises the following steps:
step 1: 400mg of Nafion film solution and polyvinylpyrrolidone are measured and dissolved in N, N-dimethylformamide, and the mass ratio of Nafion film solution, polyvinylpyrrolidone and N, N-dimethylformamide is 5:1:1, a step of; the nafion nanofiber is obtained by using an electrostatic spinning technology, and the diameter is 50-100nm.
Step 2: uniformly mixing the nafion nanofiber prepared in the step 1 with carbon-based nano platinum catalyst powder, and fully mixing under the action of strong stirring, wherein the mass ratio of the nanofiber to the catalyst powder 2 is 1:1.
step 3: and (3) coating the powder obtained in the step (2) on a proton exchange membrane with the length of 8.6cm multiplied by 8cm, and compacting to prepare the dry CCM.
The cathode and the anode are gas diffusion electrodes in the prior art, membrane electrodes are prepared, and electrochemical performance tests are carried out on a single cell evaluation device.
Under the same conditions, performance comparison is carried out with a wet membrane electrode (model BEI275V2 TMEA) in the prior art. The same conditions were set for (cathode: flow excess factor 1.8, pressure 200kpa (a), humidity RH40%, anode flow excess system 2, pressure 250kpa (a), humidity RH90%, temperature 77 ℃).
Example 2
A dry method membrane electrode preparation method of a membrane fuel cell comprises the following steps:
step 1: 400mg of Nafion film solution and polyvinylpyrrolidone are measured and dissolved in N, N-dimethylformamide, and the mass ratio of Nafion film solution, polyvinylpyrrolidone and N, N-dimethylformamide is 5:1:1, a step of; the nafion nanofiber is obtained by using an electrostatic spinning technology, and the diameter is 50-100nm.
Step 2: uniformly mixing the nafion nanofiber, the sugar powder and the carbon-based nano platinum catalyst powder prepared in the step 1, and fully mixing under the action of strong stirring, wherein the mass ratio of the nanofiber to the sugar powder to the catalyst powder 2 is 1:0.1:1.
step 3: coating the powder obtained in the step 2 on a proton exchange membrane with the length of 8.6cm multiplied by 8cm by electrostatic spraying to prepare a dry CCM;
step 4: and soaking the dry membrane electrode in water until sugar powder is dissolved, and drying.
The cathode and the anode are gas diffusion electrodes in the prior art, membrane electrodes are prepared, and electrochemical performance tests are carried out on a single cell evaluation device.
Under the same conditions, performance comparison was made with the membrane electrode prepared in example 1. The same conditions were set for (cathode: flow excess factor 1.8, pressure 200kpa (a), humidity RH40%, anode flow excess system 2, pressure 250kpa (a), humidity RH90%, temperature 77 ℃).
As shown in fig. 2, the dry electrode of example 1 has a higher operating voltage, i.e., higher power, than the wet electrode of the prior art at the same current density, and the better performance. The dry electrode of example 2 has an increased operating voltage and an increased power output of at least 10% compared to example 1 at the same current density.
The above-described preferred embodiments according to the present application are intended to suggest that, from the above description, various changes and modifications can be made by the person skilled in the art without departing from the scope of the technical idea of the present application. The technical scope of the present application is not limited to the description, but must be determined according to the scope of claims.
Claims (3)
1. A method for preparing a dry membrane electrode of a membrane fuel cell, comprising the steps of:
s1, mixing Nafion film solution, high molecular polymer and N, N-dimethylformamide according to the mass ratio of 4-10: 0.5 to 1.5:1, mixing to obtain spinning solution, and carrying out conjugate electrostatic spinning on the obtained spinning solution to obtain nafion fiber with the diameter of 10 nm-1 um; wherein the high-voltage power supply voltage of the conjugate electrostatic spinning is 1-10 kV, and the extrusion speed of the spinning solution is 0.6-1 ml h -1 ；
S2, uniformly mixing the soluble powder, the nafion fiber and the catalyst powder; the mass ratio of the nafion fiber to the catalyst powder is 1:0.5 to 5, the mass ratio of the soluble powder to the catalyst powder is 0.1 to 1:1, a step of; the soluble powder is sugar powder or polyvinyl alcohol powder;
s3, dispersing the mixture obtained in the step S2 on the surface of the proton exchange membrane, and after hot pressing or electrostatic powder spraying, dissolving and removing soluble powder in the dry membrane electrode to form pores to obtain the dry membrane electrode.
2. The method for preparing a dry membrane electrode for a membrane fuel cell according to claim 1, wherein: the high molecular polymer is formed by one or more of the following substances: polyvinylpyrrolidone, polyethylene oxide, perfluorinated sulfonic acid resin and polysulfone.
3. The method for preparing a dry membrane electrode for a membrane fuel cell according to claim 1, wherein: the catalyst powder is carbon-based nano platinum, carbon-based nano platinum cobalt alloy and iron-based powder catalyst.
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| CN202310851272.1A CN116581308B (en) | 2023-07-12 | 2023-07-12 | Dry membrane electrode preparation method of membrane fuel cell |
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| CN202310851272.1A CN116581308B (en) | 2023-07-12 | 2023-07-12 | Dry membrane electrode preparation method of membrane fuel cell |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683725A (en) * | 2012-06-07 | 2012-09-19 | 上海中科高等研究院 | Preparation method of membrane electrode assembly for direct-methanol fuel cell |
| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
| CN106848355A (en) * | 2017-02-20 | 2017-06-13 | 南京大学 | The electrostatic spinning and electrostatic spraying preparation method of a kind of membrane electrode CCM |
| CN111326752A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Solid powder of fuel cell catalyst layer and preparation method and application 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 |
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2023
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683725A (en) * | 2012-06-07 | 2012-09-19 | 上海中科高等研究院 | Preparation method of membrane electrode assembly for direct-methanol fuel cell |
| CN103441287A (en) * | 2013-08-09 | 2013-12-11 | 中国科学院上海高等研究院 | Preparation method of membrane electrode of direct methanol fuel cell |
| CN106848355A (en) * | 2017-02-20 | 2017-06-13 | 南京大学 | The electrostatic spinning and electrostatic spraying preparation method of a kind of membrane electrode CCM |
| CN111326752A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Solid powder of fuel cell catalyst layer and preparation method and application 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 |
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