CN112310416B - Method for preparing ordered fuel cell membrane electrode - Google Patents
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Abstract
The invention discloses a method for preparing an ordered fuel cell membrane electrode, which comprises the steps of selecting Teflon cloth of a special preparation process as a transfer medium, using nickel carbon as a carrier, replacing nickel in the nickel carbon with divalent platinum ions as a seed crystal for nanowire growth on the carbon carrier, growing ordered platinum nanowires from platinum nanoparticles reduced by formic acid along the platinum seed crystal, washing, drying, coating a layer of perfluorosulfonic acid proton membrane solution, and carrying out hot-pressing transfer printing to obtain a cathode of the ordered fuel cell membrane electrode; the nickel carbon is used as a growth carrier of the platinum nanowire, so that the probability of the platinum crystal growing into a wire can be increased, and the time for growing into the wire can be shortened; the layered distribution of the perfluorinated sulfonic acid proton membrane solution can reduce the coating and plugging of the seed crystal particles for the growth of the platinum nanometer, and expose more active sites for the growth of the platinum nanometer; thereby obtaining the ordered fuel cell membrane electrode with high order and excellent performance.
Description
Technical Field
The invention belongs to the field of fuel cells, and particularly relates to a method for preparing an ordered fuel cell membrane electrode.
Background
Fuel cells are clean, efficient, and long-lived power generation devices. Compared with the conventional power generation technology, the fuel cell has great advantages in the aspects of efficiency, safety, reliability, flexibility, cleanness, operability and the like, and has a very wide application prospect. As one of the fuel cells, the proton exchange membrane fuel cell also has the advantages of low operation temperature, high specific energy, long service life, high response speed, no electrolyte leakage and the like, and has good application prospects in the aspects of national defense, energy, traffic, environmental protection, communication and the like. The core component of the proton exchange Membrane fuel cell is a Membrane Electrode Assembly (MEA), which is composed of an anode, a cathode and a polymer electrolyte Membrane, wherein the Electrode (including the anode and the cathode) is composed of a diffusion layer and a catalytic layer; the diffusion layer is made of an electrically conductive porous material, and functions to support the catalytic layer, collect electric current, conduct gas, and discharge water. The catalyst layer is composed of a catalyst and a polymer electrolyte, and is a site of an electrochemical reaction. The electrochemical reaction performed in the catalytic layer is performed on a three-phase interface having the reaction gas, the protons, and the electrons at the same time, in which the reaction gas is supplied, and the electrons and the protons are conducted and transferred. The catalyst nanoparticles in the catalyst layer play a role in catalyzing and conducting electrons, the polymer electrolyte resin plays a role in conducting protons, and the micropores in the electrode play a role in transferring reactants (hydrogen and oxygen) and products (water). The best proton exchange membrane fuel cell catalyst at present is still noble metal platinum, so the platinum catalyst is an important factor for determining the performance and the manufacturing cost of the proton exchange membrane fuel cell. In order to improve the performance of the membrane electrode, it is very important to improve the structural design and preparation process of the catalyst and the catalytic layer, in addition to the development of a high-performance polymer electrolyte membrane.
The traditional catalytic layer is mainly prepared by the following three methods: one is to spray the catalyst slurry (composed of carbon-carried Pt catalyst, high-molecular electrolyte resin and solvent) on the gas diffusion layer, and dry at a certain temperature to obtain the fuel cell electrode. In this method, the polyelectrolyte resin functions as both a proton conductor and a binder; the electrolyte resin is a high molecular organic polymer that coats a part of the catalyst, so that the catalyst cannot be fully utilized. The other is to spray the uniformly mixed catalyst slurry directly onto the polymer electrolyte membrane. The method is simple and easy to implement, the electrode preparation efficiency is improved, the process flow is simplified, the catalyst is well contacted with the proton conductor polymer, but the catalyst layer has low porosity and is not beneficial to the gas diffusion process, and the utilization rate of the electrode catalyst and the three-phase reaction interface are still to be improved. And thirdly, spraying the uniformly mixed catalyst slurry on the surface of a transfer medium, heating and volatilizing the solvent to form a catalyst layer, and then transferring the catalyst layer onto the proton exchange membrane through hot pressing. In summary, the thickness of the catalyst layer obtained by the conventional preparation method is 10-20 microns, the proton conduction path and the gas diffusion path are increased, and a part of the catalyst is inevitably coated by resin, so that the part of the catalyst cannot participate in the electrochemical reaction, the utilization rate of the catalyst is reduced, and the three-phase reaction interface needs to be improved.
Patent No. CN201310011118.4 proposes a method for preparing a fuel cell membrane electrode, which comprises preparing a carbon powder substrate on a transfer medium, depositing nanowires, spraying a layer of electrolyte resin solution on the carbon powder substrate to form a catalyst layer, transferring the catalyst layer onto a proton membrane by thermal transfer to obtain a platinum nanowire catalyst layer membrane electrode, wherein the nanowires formed during the preparation of the thin catalyst layer substrate and the deposition of the platinum nanowires are disordered and easily agglomerated on the surface of a carbon black layer and deeply grown in a carbon black layer; in the hot-pressing transfer process, the condition of incomplete transfer can occur when the temperature is too low, and the selection of the transfer medium has great influence on the transfer result, thereby being not beneficial to the large-scale preparation of the platinum nanowire catalyst layer and the implementation.
Disclosure of Invention
The invention aims to provide a method for preparing an ordered fuel cell membrane electrode, which replaces nickel in nickel carbon by divalent platinum ions to be used as a seed crystal for nanowire growth, reduces the reaction time and obtains a high-performance ordered fuel cell catalyst cathode.
The preparation method of the ordered membrane electrode comprises the following steps:
the invention aims to provide a method for preparing an ordered fuel cell membrane electrode, which comprises the following steps:
step one, preparing nickel carbon: the nickel carbon is a substrate for orderly growth of the platinum nanowires, and is prepared by reducing nickel chloride hexahydrate by sodium borohydride in a normal-temperature ethanol system; weighing carbon black, adding an ethanol solution, carrying out ultrasonic dispersion in an ice-water bath for 30min, sequentially adding ethanol solutions of triethylamine and nickel chloride hexahydrate, continuing ultrasonic dispersion for 30min, dropwise adding an ethanol solution containing sodium borohydride while carrying out magnetic stirring, reacting for 1h, dropwise adding concentrated hydrochloric acid, filtering, washing, and drying in a drying oven at 60 ℃ for 3 min.
In an alkaline environment, sodium borohydride reacts with water quickly to release a large amount of hydrogen, an alkaline ethanol system is adopted in the invention, and no extra ultrapure water is added except water contained in raw materials, so that the reaction speed can be slowed down, the nickel in the obtained nickel-carbon material is distributed more uniformly and does not agglomerate, and more active sites can be provided for the platinum nanowire when the obtained nickel-carbon material is subsequently used as a growth substrate.
Secondly, preparing a growth substrate, wherein the three-dimensional composition distribution comprises a transfer medium, slurry I, slurry II and slurry III, two equal parts of dried nickel-carbon material and one part of carbon black are taken, ethanol is used as a solvent, perfluorinated sulfonic acid proton membrane solution with different mass ratios of the carbon black in the components is added to form the slurry I, the slurry II and the slurry III, ultrasonic dispersion is carried out for 30min in ice-water bath, the slurry I, the slurry II and the slurry III are sequentially and uniformly coated on transfer medium Teflon cloth, drying is carried out for 30min at 60 ℃ in a vacuum drying box to form a film with an area of 5cm and a nickel-carbon loading capacity of 0.1mg/cm, and the growth substrate is prepared2The layered structure of (3) growing a substrate.
Thirdly, growing platinum nanowires, fixing Teflon cloth loaded with a layered structure growth substrate in a culture dish, adding a solution containing 16.7-17.5g of chloroplatinic acid hexahydrate and 40mL of water into the culture dish, reacting at 40-50 ℃ for 1-2h, wherein an oxidation-reduction reaction occurs in the process, nickel in nickel carbon is replaced by chloroplatinic acid, platinum replaces the position of nickel, a seed crystal for platinum nanowire growth is formed, after the replacement reaction is finished, a large amount of divalent platinum ions are still in the solution and are not reduced, and the temperature is kept until the temperature is highCooling to 12-20 deg.C, adding 0.5-0.8mL formic acid (98 wt%), reacting for 24-48h, and reducing divalent platinum ions in the solution with formic acid to form platinum atoms, wherein the platinum atoms in the solution are more inclined to grow orderly on the layered structure growth substrate and along the platinum seed crystal, and finally depositing platinum metal loading on the substrate is 0.25mg/cm2The reaction solution is replaced, and the platinum nanowires are placed in a vacuum drying oven at 60 ℃ for 2-3 hours after being repeatedly soaked and rinsed by deionized water for many times.
Fourthly, coating a proton exchange membrane solution, adding 2-3g of perfluorosulfonic acid proton membrane solution (mass fraction is 5 wt%) into 10-15mL of ethanol solution, ultrasonically dispersing for 2-5min, and uniformly spraying the solution on ordered platinum nanowires with the loading capacity of 0.1mg/cm2And then dried at 60 ℃ for 20-30 min.
Fifthly, preparing a cathode and an anode of the membrane electrode, placing the proton exchange membrane between two transfer printing mediums, wherein one transfer printing medium is attached with a platinum nanowire catalyst, the other transfer printing medium is a blank transfer printing medium, forming a three-in-one assembly, performing hot-pressing transfer printing at the temperature of 135-145 ℃, the pressure of 0.8-1.2MPa, the time of 180s, performing hot-pressing for 100s at first, rotating for 90-180 ℃, then performing hot-pressing for 80s, cooling, and then stripping the transfer printing mediums on two sides of the proton exchange membrane to obtain the cathode of the membrane electrode assembly of the proton exchange membrane fuel cell; and weighing a commercial catalyst with low platinum loading capacity, adding ethanol and a perfluorosulfonic acid proton membrane solution to prepare slurry, and spraying the slurry on the other surface to be used as an anode to obtain the cathode and the anode of the membrane electrode of the ordered fuel cell.
Sixthly, assembling and preparing a membrane electrode: and (3) respectively attaching 5.3 × 5.3cm of SGL28BC carbon paper and a protective frame to two motor surfaces of the prepared membrane electrode assembly, and performing hot-pressing assembly to obtain the proton exchange membrane fuel cell membrane electrode.
The mass fraction of the perfluorosulfonic acid proton membrane solution is 5%.
In the first step, the carbon black is conductive carbon black and BET is 800-2/g。
The mass ratio of the ethanol to the carbon black added in the first step is 30 to 40.
In the first step, the nickel-carbon material has a nickel metal content of 1-5% and does not use a recycled platinum source.
In the first step, the addition amount of the sodium borohydride is 10-30 times of the stoichiometric ratio of the sodium borohydride required by the reduced nickel chloride.
The magnetic stirring speed in the first step is 500-1000rpH/min, and the uniformity of the oxidation-reduction reaction is directly influenced by the magnetic stirring speed.
In the first step, the addition amount of the triethylamine and the ethanol solution form 0.01-0.012mol/L, the pH value of the triethylamine is adjusted to 8-10, and the nickel carbon with more uniform distribution of the nickel simple substance on the carbon black can be obtained.
In the first step, the adding amount of the hydrochloric acid is 0.005-0.008% of the liquid volume ratio of the reaction system, the adding of the hydrochloric acid can adjust the pH value to ensure that the reaction is completely carried out, and part of nickel dissociated in the solution is adsorbed on the surface of the carbon black.
In the second step, the growth substrate is prepared by mixing slurry I and slurry II, wherein the slurry I and the slurry II are formed by mixing ethanol, nickel carbon and perfluorinated sulfonic acid proton membrane solution, and the mass ratio of the perfluorinated sulfonic acid proton membrane solution to the carbon black added in the slurry I is 10: 1; adding perfluorosulfonic acid proton membrane solution and carbon black into the slurry II according to the mass ratio of 13: 1; the slurry III is composed of ethanol, carbon black and perfluorinated sulfonic acid proton membrane solution, wherein the mass ratio of the added perfluorinated sulfonic acid proton membrane solution to the carbon black is 15: 1; the ratio of each slurry is slurry (i): slurry II: (iii) slurry (iii) =5:3:2, and total loading of 0.1mg/cm2。
The amount of ethanol solvent in the second step is 3 times of the mass of nickel carbon or carbon black.
In the second step, the preparation process of the teflon cloth comprises the following steps:
(1) coating Teflon sizing agent on the glass fiber base material layer, wherein the coating temperature is 400 ℃;
(2) baking the glass fiber substrate layer coated with the Teflon slurry at the baking temperature of 280 ℃;
(3) carrying out sodium treatment on the surface of the baked Teflon coating by adopting special Teflon surface treatment equipment, wherein the treatment temperature is 250 ℃;
(4) coating silica gel on the surface of the Teflon coating subjected to sodium treatment by using silica gel coating equipment;
the Teflon cloth has smooth surface, does not generate adsorption force when in contact with the Teflon cloth, and also has strong corrosion resistance, insulativity, pressure resistance and high temperature resistance.
In the third step, a constant humidity incubator is used for controlling the temperature, and the culture dish is not moved in the reaction process.
The invention has the beneficial effects that: the invention introduces the second metal as the seed crystal for the growth of the platinum nanowire, reduces the difficulty in the self-assembly process of directly reducing chloroplatinic acid by formic acid, forming crystal nucleus and growing the nanowire again, ensures that the reaction is easier to carry out and the result is controllable, simultaneously has low price of nickel, can reduce partial cost, can add the nickel as the second metal of the catalyst of the fuel cell, obviously improves the performance of the catalyst, and can greatly reduce the self-assembly growth time by using the seed crystal to grow the nanowire. Layering a substrate carbon black material, so that nickel carbon is positioned at the bottom of the substrate layer, divalent platinum ions preferentially displace a nickel simple substance to occupy active sites on the carbon black to form seed crystals, the platinum simple substance reduced by subsequent formic acid grows along the seed crystals, the used carbon black material has certain pores, and the platinum simple substance grows upwards along the pores to form nanowires; the layered distribution of the base layer perfluorosulfonic acid proton membrane solution has the functions of viscosity and dispersion assistance, a proper amount of perfluorosulfonic acid proton membrane solution does not wrap active sites on carbon black, and in a subsequent membrane electrode test, because a large amount of water is released in the reaction process, a catalyst layer needs certain hydrophobicity, and functional groups in the perfluorosulfonic acid proton membrane solution have certain water absorption, and the layered structure is adopted, so that the occurrence of flooding can be reduced in a single cell test, and good conductivity is achieved; the invention makes a large amount of experiments on the transfer printing condition, finally finds the experimental condition with the highest success rate, and provides greater possibility for commercial production.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is a schematic illustration of a TEM of platinum nanowires prepared by a method of preparing an ordered fuel cell membrane electrode according to the invention;
figure 2 polarization plots of the performance of membrane electrodes prepared by a method of the invention for preparing ordered fuel cell membrane electrodes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the preparation method of the ordered fuel cell membrane electrode comprises the following steps:
firstly, preparing nickel carbon with 5 percent of metal content of nickel; weighing 0.95g of carbon black, adding 32g of solution, performing ultrasonic dispersion in an ice-water bath, adding 60 mu L of triethylamine to adjust the pH value to 9, 12.34g of nickel chloride hexahydrate and 15mL of ethanol mixed solution, continuing to perform ultrasonic dispersion for 30min, then performing magnetic stirring at the speed of 800rpH/min, dropwise adding mixed solution of 7.6g of sodium borohydride and 10mL of ethanol, continuing to perform stirring reaction, dropwise adding 0.27mL of concentrated hydrochloric acid, and then filtering, washing and drying.
Step two, preparing a growth substrate: the three-dimensional composition distribution comprises a transfer medium, slurry I, slurry II and slurry III, wherein two equal parts of dry nickel carbon and one part of carbon black are taken, each part is 0.3g, 3g of ethanol is taken as a solvent, 0.64g of perfluorinated sulfonic acid proton membrane solution is added into the slurry I, 0.49g of perfluorinated sulfonic acid proton membrane solution and 0.43g of perfluorinated sulfonic acid proton membrane solution are added into the slurry II, the slurry II and the slurry III are uniformly dispersed in an ice water bath by ultrasound, then the slurry I, the slurry II and the slurry III are sequentially and uniformly coated on the transfer medium Teflon cloth, the coating area is 5cm, and the nickel carbon loading capacity is 0.1mg/cm2And finally drying the substrate in a vacuum drying oven to form the orderly grown substrate layer.
Thirdly, growing the platinum nanowires as shown in fig. 1: fixing the Teflon cloth of the basal layer in a tool clamp, adding 40mL of aqueous solution containing 16.7-17.5g of chloroplatinic acid hexahydrate into the tool clamp, reacting for 1h at 50 ℃, cooling to room temperature, adding 0.5mL of formic acid (mass fraction is 98%) at the moment, and then reacting for 24h at 18 ℃ to deposit 0.25mg/cm on the substrate2The reaction solution of the platinum nanowire is replaced, and the platinum nanowire is repeatedly soaked and rinsed by deionized water and then placed in a vacuum drying oven at the temperature of 60 ℃ for 4-6 hours.
Fourthly, coating a proton exchange membrane solution: adding 2-3g of perfluorosulfonic acid proton membrane solution (mass fraction of 5 wt%) into 10-15mL of ethanol solution, ultrasonically dispersing for 2-5min, and uniformly spraying on ordered platinum nanowires with loading capacity of 0.1mg/cm2And then dried at 60 ℃ for 20-30 min.
Fifthly, transfer printing, spraying to prepare a cathode and an anode: placing the proton exchange membrane between two transfer printing mediums, wherein one transfer printing medium is attached with a platinum nanowire catalyst, and the other transfer printing medium is blank, forming a three-in-one assembly, then hot-pressing at 135 ℃ and 0.8-1.2MPa for 180s, firstly hot-pressing for 100s, rotating for 90-180 ℃, then hot-pressing for 80s, cooling, and then stripping the transfer printing mediums at two sides of the proton exchange membrane to obtain the cathode of the membrane electrode assembly of the proton exchange membrane fuel cell; and then taking a commercial catalyst with low platinum loading capacity, adding ethanol and a perfluorosulfonic acid proton membrane solution to prepare slurry, and spraying the slurry on the other surface to be used as an anode to obtain the cathode and the anode of the membrane electrode of the ordered fuel cell.
Sixthly, assembling and preparing the MEA: and (3) respectively attaching 5.3 × 5.3cm of SGL28BC carbon paper and a protective frame to two motor surfaces of the prepared membrane electrode assembly, and performing hot-pressing assembly to obtain the proton exchange membrane fuel cell membrane electrode.
Example 2:
the preparation method of the ordered fuel cell membrane electrode comprises the following steps:
firstly, preparing nickel carbon with the metal content of nickel being 1 percent; weighing 0.99g of carbon black, adding 30g of solution, performing ultrasonic dispersion in an ice-water bath, adding 58 mu L of triethylamine to adjust the pH value to 9, mixing the solution of 2.46g of nickel chloride hexahydrate and 7.5mL of ethanol, continuing to perform ultrasonic dispersion for 30min, then performing magnetic stirring at the speed of 500rpH/min, dropwise adding the mixed solution of 1.5g of sodium borohydride and 10mL of ethanol, continuing to perform stirring reaction, dropwise adding 0.25mL of concentrated hydrochloric acid, and then filtering, washing and drying.
Step two, preparing a growth substrate: the three-dimensional composition distribution comprises a transfer medium, slurry I, slurry II and slurry III, wherein two equal parts of dry nickel carbon and one part of carbon black are taken, each part is 0.3g, 3g of ethanol is taken as a solvent, 0.64g of perfluorinated sulfonic acid proton membrane solution is added into the slurry I, 0.49g of perfluorinated sulfonic acid proton membrane solution and 0.43g of perfluorinated sulfonic acid proton membrane solution are added into the slurry II, the slurry II and the slurry III are uniformly dispersed in an ice water bath by ultrasound, then the slurry I, the slurry II and the slurry III are sequentially and uniformly coated on the transfer medium Teflon cloth, the coating area is 5cm, and the nickel carbon loading capacity is 0.1mg/cm2And finally drying the substrate in a vacuum drying oven to form the orderly grown substrate layer.
Step three, growing the platinum nanowire: fixing the Teflon cloth of the basal layer in a tool clamp, adding 40mL of aqueous solution containing 16.7-17.5g of chloroplatinic acid hexahydrate into the tool clamp, reacting for 2h at 40 ℃, cooling to room temperature, adding 0.8mL of formic acid (mass fraction is 98%) at the moment, reacting for 24h at 18 ℃, and depositing 0.25mg/cm on the substrate2The reaction solution of the platinum nanowire is replaced, and the platinum nanowire is repeatedly soaked and rinsed by deionized water and then placed in a vacuum drying oven at the temperature of 60 ℃ for 4-6 hours.
Fourthly, coating a proton exchange membrane solution: adding 2-3g of perfluorosulfonic acid proton membrane solution (mass fraction of 5 wt%) into 10-15mL of ethanol solution, ultrasonically dispersing for 2-5min, and uniformly spraying on ordered platinum nanowires with loading capacity of 0.1mg/cm2And then dried at 60 ℃ for 20-30 min.
Fifthly, transfer printing, spraying to prepare a cathode and an anode: placing the proton exchange membrane between two transfer printing mediums, wherein one transfer printing medium is attached with a platinum nanowire catalyst, and the other transfer printing medium is blank, forming a three-in-one assembly, then hot-pressing at 135 ℃ and 0.8-1.2MPa for 180s, firstly hot-pressing for 100s, rotating for 90-180 ℃, then hot-pressing for 80s, cooling, and then stripping the transfer printing mediums at two sides of the proton exchange membrane to obtain the cathode of the membrane electrode assembly of the proton exchange membrane fuel cell; and then taking a commercial catalyst with low platinum loading capacity, adding ethanol and a perfluorosulfonic acid proton membrane solution to prepare slurry, and spraying the slurry on the other surface to be used as an anode to obtain the cathode and the anode of the membrane electrode of the ordered fuel cell.
Sixthly, assembling and preparing a membrane electrode: and (3) respectively attaching 5.3 × 5.3cm of SGL28BC carbon paper and a protective frame to two motor surfaces of the prepared membrane electrode assembly, and performing hot-pressing assembly to obtain the proton exchange membrane fuel cell membrane electrode.
Example 3:
performance testing as shown in fig. 2:
table 1 membrane electrode performance tests obtained in example 1 and example 2
| Examples | Nickel loading | Formic acid | Loading of platinum metal | Power density (0.65 v) |
| Example 1 | 5% | 0.5mL | 0.25mg/cm2 | 0.89w/cm2 |
| Example 2 | 1% | 0.8mL | 0.25mg/cm2 | 0.96w/cm2 |
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A method for preparing an ordered fuel cell membrane electrode is to grow platinum nanowires by taking nickel carbon as a growth substrate as a cathode catalyst of the membrane electrode, and is characterized by comprising the following steps:
firstly, preparing nickel carbon in a pure ethanol system, weighing carbon black, adding an ethanol solution, performing ultrasonic dispersion in an ice-water bath, adding a mixed solution of triethylamine, nickel chloride hexahydrate and ethanol, performing ultrasonic dispersion for 30min, dropwise adding a mixed solution of sodium borohydride and ethanol while performing magnetic stirring, reacting for 1h, dropwise adding concentrated hydrochloric acid, filtering, washing, and drying in a vacuum drying oven at 60 ℃ for 30 min;
secondly, preparing a growth substrate, taking two equal parts of dried nickel-carbon material and one part of carbon black, taking ethanol as a solvent, adding perfluorinated sulfonic acid proton membrane solution with different mass ratios to the carbon black in each component to form slurry I, slurry II and slurry III, and carrying out super-drying in ice-water bathAfter sound dispersion for 30min, slurry I, slurry II and slurry III are sequentially and uniformly coated on transfer printing medium Teflon cloth, and the transfer printing medium Teflon cloth is dried in a vacuum drying oven at 60 ℃ for 30min to form a film with an area of 5 x 5cm and a nickel-carbon loading of 0.1mg/cm2The ordered growth substrate of (1);
thirdly, growing platinum nanowires, fixing the Teflon cloth on the basal layer in a culture dish, adding a mixed solution of 40mL of water containing 16.7-17.5g of chloroplatinic acid hexahydrate into the culture dish, reacting for 1-2h at 40-50 ℃, adding 0.5-0.8mL of formic acid with the mass fraction of 98% after cooling to 12-20 ℃, reacting for 24-48h, and depositing 0.25mg/cm of formic acid on the substrate2The reaction solution of the platinum nanowire is replaced, and the platinum nanowire is placed in a vacuum drying oven at 60 ℃ for 4-6 hours after being repeatedly soaked and rinsed by deionized water for many times;
fourthly, coating proton exchange membrane solution, adding 2-3g of perfluorinated sulfonic acid proton membrane solution into 10-15mL of ethanol solution, ultrasonically dispersing for 2-5min, and uniformly spraying the solution on ordered platinum nanowires with the coating amount of 0.1mg/cm2Then drying at 60 ℃ for 20-30 min;
fifthly, preparing the cathode and the anode of the membrane electrode: placing the proton exchange membrane between two transfer printing mediums, wherein one transfer printing medium is attached with a platinum nanowire catalyst, the other transfer printing medium is blank, forming a three-in-one assembly, performing hot-pressing transfer printing at the temperature of 135-; then taking a catalyst with low platinum loading capacity, adding ethanol and perfluorosulfonic acid proton membrane solution to prepare slurry, spraying the slurry on the other surface to be used as an anode, wherein the platinum loading capacity is 0.15mg/cm2Obtaining the cathode and the anode of the membrane electrode of the ordered fuel cell;
sixthly, assembling and preparing the MEA: and respectively attaching 5.3 x 5.3cm carbon paper and a protective frame to the cathode and the anode of the prepared membrane electrode assembly, and performing hot-pressing assembly to obtain the proton exchange membrane fuel cell membrane electrode.
2. The method of making an ordered fuel cell membrane electrode assembly according to claim 1Characterized in that the carbon black in the first step is conductive carbon black, and BET is 800-2/g。
3. The method of making an ordered fuel cell membrane electrode assembly according to claim 1 wherein the mass ratio of ethanol to carbon black in the first step is 30 to 40 times.
4. The method of making an ordered fuel cell membrane electrode assembly according to claim 1 wherein the nickel carbon material in said first step has a nickel metal content of 1-5%.
5. The method of making an ordered fuel cell membrane electrode assembly according to claim 1 wherein the amount of sodium borohydride added in the first step is 10-30 times the stoichiometric ratio of reduced nickel chloride sodium borohydride.
6. The method for preparing the membrane electrode of the ordered fuel cell according to claim 1, wherein the amount of the triethylamine added in the first step is 0.01-0.012mol/L in substance concentration in the solution system, and the pH value is adjusted by the triethylamine to be 8-10.
7. The method of claim 1 wherein the magnetic stirring in the first step is 500-1000 rph/min.
8. The method for preparing an ordered fuel cell membrane electrode assembly according to claim 1, wherein the amount of said hydrochloric acid added in the first step is 0.005-0.008% by volume of the reaction system liquid.
9. The method of claim 1, wherein the teflon cloth is prepared by the following steps:
(1) coating Teflon sizing agent on the glass fiber base material layer, wherein the coating temperature is 400 ℃;
(2) baking the glass fiber substrate layer coated with the Teflon slurry at the baking temperature of 280 ℃;
(3) carrying out sodium treatment on the surface of the baked Teflon coating by adopting special Teflon surface treatment equipment, wherein the treatment temperature is 250 ℃;
(4) and coating silica gel on the surface of the Teflon coating subjected to sodium treatment by using silica gel coating equipment.
10. The method for preparing the membrane electrode of the ordered fuel cell according to claim 1, wherein in the second step, the growth substrate is prepared by mixing slurry (I) and slurry (II) with ethanol, nickel carbon and perfluorinated sulfonic acid proton membrane solution, wherein the mass ratio of the perfluorinated sulfonic acid proton membrane solution to carbon black added in the slurry (I) is 10: 1; adding perfluorosulfonic acid proton membrane solution and carbon black into the slurry II according to the mass ratio of 13: 1; the slurry III is composed of ethanol, carbon black and perfluorinated sulfonic acid proton membrane solution, wherein the mass ratio of the added perfluorinated sulfonic acid proton membrane solution to the carbon black is 15: 1; the ratio of each slurry is slurry (i): slurry II: (iii) slurry (iii) =5:3:2, and total loading of 0.1mg/cm2。
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