CN110534779A - A kind of enhanced membrane electrode of non-fluorinated polymer and preparation method thereof - Google Patents

A kind of enhanced membrane electrode of non-fluorinated polymer and preparation method thereof Download PDF

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CN110534779A
CN110534779A CN201910772708.1A CN201910772708A CN110534779A CN 110534779 A CN110534779 A CN 110534779A CN 201910772708 A CN201910772708 A CN 201910772708A CN 110534779 A CN110534779 A CN 110534779A
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polymer
exchange resin
membrane electrode
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catalyst
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CN110534779B (en
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赵阳
李雪
王树博
谢晓峰
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • 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]
    • 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
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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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Abstract

The present invention relates to enhanced membrane electrode of a kind of non-fluorinated polymer and preparation method thereof, the enhancement layer based on non-fluorinated polymer and the polyelectrolyte floor based on ion exchange resin are placed in gas-diffusion electrode surface with deposition pattern, are then assembled into membrane electrode.The present invention changes the existence form of conventional polymer electrolyte and its enhancement layer, it is added in the preparation process of membrane electrode as a solution, ultimately forms integrated film electrode.This enhanced membrane electrode of non-fluorinated polymer and preparation method thereof is not only avoided that aromatic polymer and perfluorinated sulfonic resin in the incompatible problem of structure, but also can control the thickness of enhancement layer and polymer dielectric film.

Description

A kind of enhanced membrane electrode of non-fluorinated polymer and preparation method thereof
Technical field
The invention belongs to the technical fields of fuel cell, and in particular to a kind of enhanced membrane electrode of non-fluorinated polymer and its system Preparation Method.
Background technique
Fuel cell is a kind of power generator of electrochemistry, and the chemical energy of fuel and oxidant directly can be passed through electrode by it Reaction is converted into electric energy.Compared with traditional generation mode, the energy conversion of fuel cell is directly, to need not move through thermal energy This link is converted, therefore generating efficiency is relatively high.Its electricity generating principle occurs as other electrochmical power sources in the anode of battery The catalytic reduction reaction of oxidant occurs for the catalytic oxidation of fuel, cathode.Electrolyte separates anode and cathode and provides proton and moves Mobile Communication road, electronics drive load acting by external circuit, thus constitute battery loading circuit.When battery operation, fuel It is continuously fed to battery in a steady stream with oxidant, the unreacted fuel of reaction product and part and oxidant are had after electrochemical reaction Discharge, while being accompanied by heat generation.
Membrane electrode assembly is the core component of electrochemical reaction, by anode and cathode Catalytic Layer and polymer electrolyte diaphragm group At.Membrane electrode is the main place that electrochemical reaction occurs for fuel and oxygen, and the performance of membrane electrode directly determines fuel cell Function and efficiency.The most directly effective a kind of mode for improving membrane electrode performance at present is to reduce film thickness.First, film thickness Reduction can directly reduce fuel cell ohmage, to reduce ohmic polarization；Second, the reduction of film thickness, so that negative The back-diffusion that pole generates water becomes easy, and can satisfy the requirement of membrane electrode from humidification under low moisture environments；Third, in fuel electricity Under the high current working condition in pond, cathode caused by film thickness reduces, which generates water back-diffusion, can also reduce the discharge pressure of cathode, To reduce the water logging bring loss of voltage.But the reduction of film thickness has two big influences to the preparation of membrane electrode and use.One It is the reduction of film thickness, so that traditional method for preparing membrane electrode is difficult to carry out, such as GDE method and CCM method, needs to explore new work Skill meets the preparation of ultrathin membrane membrane electrode；Second is that the reduction of film thickness will increase hydrogen infiltration electric current and internal short-circuit circuit, Battery life is influenced, needs to limit membrane swelling by introducing enhancement layer, reduce hydrogen infiltration.
The enhanced polymer electrolyte in membrane electrode uses fluorinated polymer as reinforcement material more at present, such as poly- Tetrafluoroethene etc..But the disadvantages of fluorinated polymer is with high costs, and glass transition temperature is low and processing difficulties, limits The development of fuel cell.At the same time, non-fluorinated polymer, such as polyether-ketone, polyether sulfone, polyimides etc., due to raw material is easy to get, Low in cost, the advantages that heat resisting temperature is high, it is increasingly becoming the alternative materials of fluorinated polymer.At present using aromatic polymer as The Major Difficulties of polymer dielectric reinforcement material are: aromatic polymer and perfluorinated sulfonic resin exist not in structure Compatibility；Due to technical problem, ultra-thin porous type aromatic polymer enhancement layer is difficult to prepare.Therefore, non-fluorinated polymer conduct The membrane electrode of enhancement layer is not yet applied.
Summary of the invention
In order to solve the problems in the existing technology, a kind of enhanced membrane electrode of non-fluorinated polymer provided by the invention and Preparation method is a kind of novel membrane electrode technology of preparing, change conventional polymer electrolyte and its enhancement layer there are shapes It is added in the preparation process of membrane electrode by formula as a solution, ultimately forms integrated film electrode.This non-fluorine polymerization Enhanced membrane electrode of object and preparation method thereof is both avoided that aromatic polymer and perfluorinated sulfonic resin are asked structure is incompatible Topic, and can control the thickness of enhancement layer and polymer dielectric film.There has been no the pertinent literature reports of the type membrane electrode at present Road.
The present invention adopts the following technical scheme that, a kind of enhanced membrane electrode of non-fluorinated polymer, the increasing based on non-fluorinated polymer Strong layer and the polyelectrolyte floor based on ion exchange resin are placed in gas-diffusion electrode surface with deposition pattern, then It is assembled into membrane electrode.Reinforcement material and membrane material selectable range are wide, and enhancement layer and polyelectrolyte floor thickness are accurate Controllably.
In the preferred embodiments of the present invention, the reinforcement material is non-fluorinated polymer material, including polyethers Sulfone quasi polymer, polyether-ketone quasi polymer, polyimide-based polymer, polynorbornene quasi polymer, polyolefin polymers, One or more of polycarbonate polymer, poly (arylene ether nitrile), polyarylether phosphine oxide；The ion exchange resin include yin from Sub-exchange resin and cation exchange resin；Wherein, the anion exchange resin includes perfluor anionoid polymer, gathers virtue Ethers anionic polymer, polyolefins anionic polymer, poly aryl ketone anionoid polymer, polynorbornene anionoid One or more of polymer；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonated polyether Type of Collective Object, sulfonated polyolefin quasi polymer, sulfonation poly aryl ketone quasi polymer, one or more of sulfonation polynorbornene class.
In the preferred embodiments of the present invention, reinforcement material is deposited on to gas diffusion electricity in the form of electrostatic spinning Pole surface；By the solution of ion exchange resin to spray, transfer, chemical deposition, electrochemical deposition method, sputter deposition One of method, dry powder gunite, impact system deposit on enhancement layer, are then assembled into membrane electrode.
In the preferred embodiments of the present invention, the preparation method of the enhanced membrane electrode of the non-fluorinated polymer, packet Include that specific step is as follows:
(1) catalyst is add to deionized water, is stirred evenly, after solvent dilution is added, ultrasonic disperse under ice-water bath is made Catalyst solution；
(2) ion exchange resin is added in the catalyst solution in step (1), ultrasonic disperse, catalyst pulp is made；
(3) catalyst pulp in step (2) is deposited into gas diffusion layer surface；
(4) solution of non-fluorinated polymer is deposited on the resulting double-deck gas-diffusion electrode of step (3) by electrostatic spinning technique Surface；
It (5) will be on the liquid deposition of ion exchange resin to step (4) resulting electrostatic spinning；
(6) the resulting half-cell hot pressing of step (5) is obtained into membrane electrode.
In the preferred embodiments of the present invention, in step (1), the catalyst includes platinum based catalyst, alloy Class catalyst and non-precious metal catalyst.
In the preferred embodiments of the present invention, in step (1), the solvent is alcohol compound；The alcohol Class compound includes methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, one or more of isopropanol.
In the preferred embodiments of the present invention, in step (1), the catalyst solution includes that catalyst is 7-8 Part, deionized water is 100-500 parts, and alcohol compound is 5000-10000 parts.
In the preferred embodiments of the present invention, in step (1), the ion exchange resin includes anion exchange Resin and cation exchange resin；The anion exchange resin includes perfluor anionoid polymer, polyarylether anionoid Polymer, polyolefins anionic polymer, poly aryl ketone anionoid polymer, in polynorbornene anionoid polymer It is one or more of；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonated polyether quasi polymer, sulfonation polyene Hydrocarbon polymer, sulfonation poly aryl ketone quasi polymer, one or more of sulfonation polynorbornene class.
In the preferred embodiments of the present invention, in step (1), the time of the stirring is 10-200 minutes；Institute The time for the ultrasonic disperse stated is 10-200 minutes.
In the preferred embodiments of the present invention, the mass ratio of the catalyst and ion exchange resin is 3-4:1.
In the preferred embodiments of the present invention, in step (2), the time of the ultrasonic disperse is 10-200 points Clock.
In the preferred embodiments of the present invention, in step (3), the deposition method includes spraying, transfer, changes Learn one of sedimentation, electrochemical deposition method, sputter deposition method, dry powder gunite, impact system.
In the preferred embodiments of the present invention, in step (4), the non-fluorinated polymer includes polyether sulfone polymerization Object, polyether-ketone quasi polymer, polyimide-based polymer, polynorbornene quasi polymer, polyolefin polymers, polycarbonate One or more of quasi polymer, poly (arylene ether nitrile), polyarylether phosphine oxide.
In the preferred embodiments of the present invention, in step (4), the electrospinning parameters include solution concentration 3- 35wt.%, spinning duration 0.5-10 minutes.
In the preferred embodiments of the present invention, in step (5), the ionomer includes anion exchange tree Rouge and cation exchange resin；The anion exchange resin includes perfluor anionoid polymer, and polyarylether anionoid is poly- Close object, polyolefins anionic polymer, poly aryl ketone anionoid polymer, one in polynorbornene anionoid polymer Kind is several；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonated polyether quasi polymer, sulfonated polyolefin Quasi polymer, sulfonation poly aryl ketone quasi polymer, one or more of sulfonation polynorbornene class.
In the preferred embodiments of the present invention, in step (5), the deposition method includes spraying, transfer, changes Learn one of sedimentation, electrochemical deposition method, sputter deposition method, dry powder gunite, impact system.
In the preferred embodiments of the present invention, in step (6), the hot pressing time is 1-10 minutes, hot pressing temperature Degree is 80-160oC。
Compared with traditional membrane electrode, the invention has the following beneficial effects:
1, membrane electrode prepared by the present invention has double-deck enhancement layer, can be effectively reduced the hydrogenation electric current density of membrane electrode, is promoted Improve the membrane electrode service life while membrane electrode performance.
2, in membrane electrode prepared by the present invention, reinforcement material, polymer electrolyte type selectable range are wide in range, Enhancement layer thickness, polyelectrolyte floor thickness controllable precise.
3, preparation process simple process of the invention, safety and environmental protection is low in cost, saves reinforcement and membrane material Production technology can be applicable.
Detailed description of the invention
It is described further with reference to the accompanying drawing:
Fig. 1 is membrane electrode schematic cross-section in example 1 and sweeps electron microscopic picture.Polyether sulfone fiber layer is high-visible, close to Catalytic Layer Humidification is played to polyelectrolyte floor in side.
Fig. 2 is polarization curve, alternating-current resistance and the power density comparative situation of membrane electrode in example 1.From film in figure Electrode is the membrane electrode of (embodiment 1) of the invention preparation, and conventional membrane electrode is to be based on 211 film of Nafion to use CCM legal system Standby membrane electrode.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this Invention is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, without structure At limitation of the present invention.
Embodiment 1
1, the Catalytic Layer slurry configuration based on perfluorinated sulfonic resin:
According to mass ratio, 7 parts of Pt/C catalyst, 3 parts of perfluorinated sulfonic resin, 100 parts of deionized water, the ratio system that 5000 parts of solvent Standby Catalytic Layer slurry, wherein perfluorinated sulfonic resin is Nafion resin, and solvent is ethyl alcohol.
2, the preparation of gas-diffusion electrode
Catalyst pulp ultrasound is sprayed on gas diffusion layer surface.By controlling spray time, gas-diffusion electrode is controlled Catalyst loading is respectively 0.2 mg/cm2(anode) and 0.4mg/cm2(cathode).
3, the preparation of polyether sulfone enhancement layer
By polyether sulfone polymer electrostatic spinning on gas-diffusion electrode surface.Polyether sulfone solution concentration is 15%, solvent N, N- bis- The mixed solvent of methylformamide and acetone；The electrostatic spinning time is 2 minutes.
4, the preparation of polyelectrolyte floor
Perfluor sulfoacid resin solution ultrasound is sprayed on electrostatic spinning layer.By controlling spray time, control resin supports only Amount is in 2.0mg/cm2。
5, membrane electrode hot pressing
Resulting anode and cathode half-cell hot pressing is obtained into membrane electrode, hot pressing time is 3 minutes, hot pressing temperature 140oC。
6, monocell assembling and test
The membrane electrode assembly of preparation is dressed up into monocell, effective affecting acreage 5cm2；
The test condition of polarization curve are as follows: hydrogen/oxygen, back pressure 2.5bar, 80 DEG C of battery temperature, anode and cathode relative humidity 30%, Gas excess coefficient: anode 1.25, cathode 2.0；It is executed using the testing standard of U.S. DOE.
Test results are shown in figure 2, and under the same test conditions, the membrane electrode performance prepared using technology of the invention is excellent In the membrane electrode of traditional CCM method preparation, and the internal resistance of cell is relatively low.
Embodiment 2
1, the Catalytic Layer slurry configuration based on sulfonated polyether sulphone resin:
According to mass ratio, 7 parts of Pt/C catalyst, 3 parts of sulfonate resin, 100 parts of deionized water, the ratio preparation that 5000 parts of solvent is urged Change layer slurry, wherein perfluorinated sulfonic resin is sulfonated polyether sulphone resin, and solvent is ethyl alcohol.
2, the preparation of gas-diffusion electrode
Catalyst pulp ultrasound is sprayed on gas diffusion layer surface.By controlling spray time, gas-diffusion electrode is controlled Catalyst loading is respectively 0.2 mg/cm2(anode) and 0.4mg/cm2(cathode).
3, the preparation of polyether sulfone enhancement layer
By polyether sulfone polymer electrostatic spinning on gas-diffusion electrode surface.Polyether sulfone solution concentration is 15%, solvent N, N- bis- The mixed solvent of methylformamide and acetone；The electrostatic spinning time is 2 minutes.
4, the preparation of polyelectrolyte floor
Sulfonated polyether sulfone resin solution ultrasound is sprayed on electrostatic spinning layer.By controlling spray time, control resin is carried on a shoulder pole only Carrying capacity is in 2.0mg/cm2。
5, membrane electrode hot pressing
Resulting anode and cathode half-cell hot pressing is obtained into membrane electrode, hot pressing time is 3 minutes, hot pressing temperature 140oC。
6, monocell assembling and test
The membrane electrode assembly of preparation is dressed up into monocell, effective affecting acreage 5cm2；
The test condition of polarization curve are as follows: hydrogen/oxygen, back pressure 2.5bar, 80 DEG C of battery temperature, anode and cathode relative humidity 30%, Gas excess coefficient: anode 1.25, cathode 2.0；It is executed using the testing standard of U.S. DOE.
Embodiment 3
1, the Catalytic Layer slurry configuration based on alkalescence anion-exchange resin:
According to mass ratio, 7 parts of Pt/C catalyst, 3 parts of anion exchange resin, 100 parts of deionized water, the ratio that 5000 parts of solvent Catalytic Layer slurry is prepared, wherein anion exchange resin is FuMA-Tech anion exchange resin, and solvent is ethyl alcohol.
2, the preparation of gas-diffusion electrode
Catalyst pulp ultrasound is sprayed on gas diffusion layer surface.By controlling spray time, gas-diffusion electrode is controlled Catalyst loading is respectively 0.2 mg/cm2(anode) and 0.4mg/cm2(cathode).
3, the preparation of polyether sulfone enhancement layer
By polyether sulfone polymer electrostatic spinning on gas-diffusion electrode surface.Polyether sulfone solution concentration is 15%, solvent N, N- bis- The mixed solvent of methylformamide and acetone；The electrostatic spinning time is 2 minutes.
4, the preparation of polyelectrolyte floor
Fuma-tech anion exchange resin solution ultrasound is sprayed on electrostatic spinning layer.By controlling spray time, control The net loading of resin is in 2.0mg/cm2。
5, membrane electrode hot pressing
Resulting anode and cathode half-cell hot pressing is obtained into membrane electrode, hot pressing time is 3 minutes, hot pressing temperature 100oC。
6, monocell assembling and test
The membrane electrode assembly of preparation is dressed up into monocell, effective affecting acreage 5cm2；
The test condition of polarization curve are as follows: hydrogen/oxygen, back pressure 2.5bar, 80 DEG C of battery temperature, anode and cathode relative humidity 30%, Gas excess coefficient: anode 1.25, cathode 2.0；It is executed using the testing standard of U.S. DOE.
Embodiment 4
1, the Catalytic Layer slurry configuration based on quaternary ammonium salt type polyether sulphone resin:
According to mass ratio, 7 parts of Pt/C catalyst, 3 parts of anion exchange resin, 100 parts of deionized water, the ratio that 5000 parts of solvent Catalytic Layer slurry is prepared, wherein anion exchange resin is quaternary ammonium salt type polyether sulphone resin, and solvent is ethyl alcohol.
2, the preparation of gas-diffusion electrode
Catalyst pulp ultrasound is sprayed on gas diffusion layer surface.By controlling spray time, gas-diffusion electrode is controlled Catalyst loading is respectively 0.2 mg/cm2(anode) and 0.4mg/cm2(cathode).
3, the preparation of enhancement layer
By polyether sulfone polymer electrostatic spinning on gas-diffusion electrode surface.Polyether sulfone solution concentration is 15%, solvent N, N- bis- The mixed solvent of methylformamide and acetone；The electrostatic spinning time is 2 minutes.
4, the preparation of polyelectrolyte floor
Quaternary ammonium salt type polyether sulphone resin solution ultrasound is sprayed on electrostatic spinning layer.By controlling spray time, resin is controlled Net loading is in 2.0mg/cm2。
5, membrane electrode hot pressing
Resulting anode and cathode half-cell hot pressing is obtained into membrane electrode, hot pressing time is 3 minutes, hot pressing temperature 100oC。
6, monocell assembling and test
The membrane electrode assembly of preparation is dressed up into monocell, effective affecting acreage 5cm2；
The test condition of polarization curve are as follows: hydrogen/oxygen, back pressure 2.5bar, 80 DEG C of battery temperature, anode and cathode relative humidity 30%, Gas excess coefficient: anode 1.25, cathode 2.0；It is executed using the testing standard of U.S. DOE.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art 's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed Range.

Claims (10)

1. a kind of enhanced membrane electrode of non-fluorinated polymer, which is characterized in that enhancement layer based on non-fluorinated polymer and based on from The polyelectrolyte floor of sub-exchange resin is placed in gas-diffusion electrode surface with deposition pattern, is then assembled into membrane electrode.
2. membrane electrode according to claim 1, which is characterized in that the reinforcement material is non-fluorinated polymer material, Including polyether sulfone polymer, polyether-ketone quasi polymer, polyimide-based polymer, polynorbornene quasi polymer, polyolefin One or more of quasi polymer, polycarbonate polymer, poly (arylene ether nitrile), polyarylether phosphine oxide；The amberlite Rouge includes anion exchange resin and cation exchange resin；Wherein, the anion exchange resin includes perfluor anionoid Polymer, polyarylether anionoid polymer, polyolefins anionic polymer, poly aryl ketone anionoid polymer gather drop ice One or more of piece alkenes anionic polymer；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonation Polyarylether polymer, sulfonated polyolefin quasi polymer, sulfonation poly aryl ketone quasi polymer, one of sulfonation polynorbornene class Or it is several.
3. membrane electrode according to claim 1, which is characterized in that reinforcement material is deposited on gas in the form of electrostatic spinning Body diffusion electrode surface；By the solution of ion exchange resin to spray, transfer, chemical deposition, electrochemical deposition method, physics splashes It penetrates one of sedimentation, dry powder gunite, impact system to deposit on enhancement layer, is then assembled into membrane electrode.
4. the preparation method of the enhanced membrane electrode of non-fluorinated polymer of any of claims 1-3, which is characterized in that packet Include that specific step is as follows:
(1) catalyst is add to deionized water, is stirred evenly, after solvent dilution is added, ultrasonic disperse under ice-water bath is made Catalyst solution；
(2) ion exchange resin is added in the catalyst solution in step (1), ultrasonic disperse, catalyst pulp is made；
(3) catalyst pulp in step (2) is deposited into gas diffusion layer surface；
(4) solution of non-fluorinated polymer is deposited on the resulting double-deck gas-diffusion electrode of step (3) by electrostatic spinning technique Surface；
It (5) will be on the liquid deposition of ion exchange resin to step (4) resulting electrostatic spinning；
(6) the resulting half-cell hot pressing of step (5) is obtained into membrane electrode.
5. the preparation method according to claim 4, which is characterized in that in step (1), the catalyst includes that platinum base is urged Agent, alloy type catalyst and non-precious metal catalyst；The solvent is alcohol compound；The alcohol compound packet Include methanol, ethyl alcohol, ethylene glycol, normal propyl alcohol, one or more of isopropanol；The catalyst solution includes that catalyst is 7- 8 parts, deionized water is 100-500 parts, and alcohol compound is 5000-10000 parts；The ion exchange resin includes anion Exchanger resin and cation exchange resin；The anion exchange resin includes perfluor anionoid polymer, polyarylether class yin Ionomer, polyolefins anionic polymer, poly aryl ketone anionoid polymer, polynorbornene anionoid polymer One or more of；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonated polyether quasi polymer, sulfonation Polyolefin polymers, sulfonation poly aryl ketone quasi polymer, one or more of sulfonation polynorbornene class；The stirring Time is 10-200 minutes；The time of the ultrasonic disperse is 10-200 minutes.
6. the preparation method according to claim 4, which is characterized in that the quality of the catalyst and ion exchange resin Than for 3-4:1.
7. the preparation method according to claim 4, which is characterized in that in step (2), the time of the ultrasonic disperse is 10-200 minutes；In step (3), the deposition method includes spraying, transfer, chemical deposition, electrochemical deposition method, object Manage one of sputtering method, dry powder gunite, impact system.
8. the preparation method according to claim 4, which is characterized in that in step (4), the non-fluorinated polymer includes poly- Ether sulfone quasi polymer, polyether-ketone quasi polymer, polyimide-based polymer, polynorbornene quasi polymer, polyolefins polymerization One or more of object, polycarbonate polymer, poly (arylene ether nitrile), polyarylether phosphine oxide；The electrospinning parameters include Solution concentration 3-35wt.%, spinning duration 0.5-10 minutes.
9. the preparation method according to claim 4, which is characterized in that in step (5), the ionomer includes yin Ion exchange resin and cation exchange resin；The anion exchange resin includes perfluor anionoid polymer, polyarylether Anionoid polymer, polyolefins anionic polymer, poly aryl ketone anionoid polymer, polynorbornene anionoid are poly- Close one or more of object；The cation exchange resin includes perfluorinated sulfonic acid quasi polymer, sulfonated polyether quasi polymer, Sulfonated polyolefin quasi polymer, sulfonation poly aryl ketone quasi polymer, one or more of sulfonation polynorbornene class；Described is heavy Product method include spraying, transfer, chemical deposition, electrochemical deposition method, sputter deposition method, dry powder gunite, One of impact system.
10. the preparation method according to claim 4, which is characterized in that in step (6), the hot pressing time is 1-10 Minute, hot pressing temperature 80-160oC。
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