CN111564641B - Preparation method of catalyst layer in membrane electrode - Google Patents

Preparation method of catalyst layer in membrane electrode Download PDF

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CN111564641B
CN111564641B CN202010457108.9A CN202010457108A CN111564641B CN 111564641 B CN111564641 B CN 111564641B CN 202010457108 A CN202010457108 A CN 202010457108A CN 111564641 B CN111564641 B CN 111564641B
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carbon black
catalyst layer
catalyst
conductive carbon
noble metal
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CN111564641A (en
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刘征
陈孟杰
舒正龙
乔红艳
陈启章
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Sinocat Environmental Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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

Abstract

The invention relates to the field of new energy materials and application in fuel cell automobiles, in particular to a preparation method of a catalyst layer in a membrane electrode. Compared with the prior art, the catalyst layer comprises a polyamide-amine dendrimer coated nano noble metal catalyst and surface functionalized conductive carbon black, and the catalyst layer has the beneficial effects that: the polyamide-amine dendrimer is used as a template agent, so that the structure, size and distribution of the nano particles of the catalyst can be better controlled at the atomic and molecular levels, and the utilization rate of noble metal can be greatly improved, thereby improving the performance of the fuel cell and reducing the cost; the surface functionalized conductive carbon black and PGM-DENC are covalently cross-linked through amide to form PGM (C) -DENC, so that the conductivity of the catalyst is improved.

Description

Preparation method of catalyst layer in membrane electrode
Technical Field
The invention relates to the field of new energy materials and application in fuel cell automobiles, in particular to a preparation method of a catalyst layer in a membrane electrode.
Background
A fuel cell is a power generation device that directly converts chemical energy thereof into electric energy without a combustion process, electrochemical reactions occur at electrodes on both sides, and an electrocatalyst coated on the electrodes is used to promote an electrochemical oxidation reaction of fuel occurring at an anode and a reduction reaction of oxygen occurring at a cathode. Among the Fuel cells, Proton Exchange Membrane (PEM) Fuel cells (PEMFC) have recently received wide market attention due to their characteristics of high power density, fast start-up speed, low operating temperature, and environmental friendliness. The energy density is high, the starting speed is high, the low-temperature stable operation is realized, the operation temperature is low, the environment is friendly, and the like, so that the energy-saving power supply is very suitable for serving as a power source of an electric automobile, a portable small power supply, a power supply of an underwater power system, and the like. Therefore, since the nineties of the last century, the technology has been rapidly developed due to the wide attention of governments and energy sources, automobiles, household appliances, military industry and the like.
The Membrane Electrode Assembly (MEA) is the main part of the proton exchange membrane fuel cell, and comprises a five-layer structure, wherein the central layer is a proton exchange membrane, two catalyst layers separated by a membrane are arranged on two sides of the central layer to form a catalytic membrane electrode with a cathode and an anode, and the catalytic membrane electrode plays an important role in the process of converting the chemical energy of the fuel cell into the electric energy; there are two gas diffusion layers outside the catalytic membrane electrode, which are mainly used to transport reactants (fuel, air) to the membrane electrode and remove the product-water.
In the current commercial membrane electrode assembly, the catalyst layer is mostly made of the traditional precious metal (PGM) Pt/C electrocatalyst, but the precious metal has limited reserves on the earth, is expensive, has low utilization rate in the fuel cell, and hinders the commercialization process of the proton exchange membrane fuel cell. Over the past several decades, numerous researchers have been working on new generation membrane electrode assemblies and catalyzed membrane electrodes with high efficiency, low precious metal (PGM), high durability. Based on the aim, the invention provides a catalytic membrane electrode and a preparation method of a catalyst layer, which is a key component of the catalytic membrane electrode, through a novel high-efficiency catalyst synthesis technology, aims to improve the performance of the catalytic membrane electrode of the fuel cell and reduce the cost, and provides a novel process technical route for key parts of the fuel cell, the catalytic membrane electrode and the catalyst layer thereof.
Disclosure of Invention
The invention aims to overcome the defects of high consumption and low utilization rate of noble metals in a proton exchange membrane fuel cell in the prior art, and provides a catalyst layer, slurry, a preparation method and a catalytic membrane electrode (CCM) prepared by the catalyst layer and the slurry.
The invention provides the following technical scheme:
a catalyst layer comprises a nano noble metal catalyst and conductive carbon black, the mass ratio of the conductive carbon black to the nano noble metal catalyst is 0.01% -1%, preferably 0.1% -0.5%, the nano noble metal catalyst is a polyamide-amine dendrimer coated nano noble metal catalyst, and the conductive carbon black is surface functionalized conductive carbon black.
The purpose of the functionalization of the conductive carbon black is to more effectively bind with the catalyst, thereby increasing the conductivity of the catalyst.
According to the invention, the polyamide-amine dendrimer is used as a template agent and a stabilizer, the prepared catalyst layer has a controllable nano structure and particle size, and the utilization rate of noble metals is improved; the conductivity of the catalyst is improved by modifying the conductive carbon black.
Wherein, the nanometer noble metal catalyst is prepared by the following method: and (2) carrying out a complex reaction on the polyamide-amine dendrimer and a noble metal compound, adding a reducing agent for a reduction reaction, and separating, washing and drying to obtain the nano noble metal catalyst wrapped by the polyamide-amine dendrimer.
Specifically, according to the method reported in the literature, a commercial polyamidoamine dendrimer is subjected to pretreatment and then redispersed in deionized water to form an aqueous solution with a certain concentration, then a certain PGM/PAMAM molar ratio (the ratio is more than 40) and a certain concentration of noble metal acid or salt aqueous solution are added under stirring until metal ions are completely complexed by the PAMAM dendrimer to form metal ions wrapped in the PAMAM dendrimer, and then excessive NaBH is added dropwise under vigorous stirring at a certain temperature (0-25 ℃), so that the PAMAM dendrimer is dissolved in the aqueous solution4(0.3-0.5M in 0.1-0.3M NaOH), and stirring until the noble metal ions are completely reduced, separating, washing and drying the obtained solution to finally obtain the Dendrimer-coated Nano metal Catalyst, which is defined as PGM-DENC (Dendrimer-Encapsulated-Nano-Catalyst), and repeating the above technical route to obtain the required particle size of the nanoparticles.
Preferably, the conductive carbon black is prepared by the following method: adding conductive carbon black into an acid solution for acidification treatment, then carrying out esterification or anhydride modification on the conductive carbon black, separating, washing and filtering, and drying the obtained filtrate to obtain the surface functionalized conductive carbon black.
A slurry for preparing a catalyst layer is characterized by comprising a nano noble metal catalyst and conductive carbon black, and further comprising an ion cross-linked polymer (Ionermer) and isobutanol serving as a solvent.
Preferably, the slurry for preparing the catalyst layer is prepared by the steps of:
PGM-DENC and surface functionalized conductive carbon black are added into N-hydroxysuccinimide (NHS) aqueous solution, and are stirred to react to obtain a carbon-modified polyamide-amine dendrimer coated nano noble metal catalyst, which is named PGM (C) -DENC, and the PGM-DENC is ultrasonically dispersed in deionized water, and then Isobutanol (IPA) solvent and ion cross-linked polymer (Ionermer) solution are added, wherein the ion cross-linked polymer used in the invention is 10 wt.% aqueous solution of perfluorosulfonic acid (Nafion), and finally the isobutanol solvent is supplemented and is sequentially added into the deionized water in a dropwise manner, and the catalyst layer slurry is stirred to react to obtain the catalyst layer slurry.
Preferably, another preparation method of the slurry for preparing the catalyst layer is as follows:
ultrasonically dispersing PGM-DENC in deionized water, then adding the deionized water in the order of firstly an isobutanol solvent and then a solution of an ionomer (Ionermer), uniformly stirring, adding an N-hydroxysuccinimide (NHS) aqueous solution containing surface functionalized conductive carbon black, then supplementing and adding the isobutanol solvent, and stirring to obtain catalyst layer slurry.
Preferably, the mass ratio of the ionomer (ionirmer) to the surface-functionalized conductive carbon black particles is 0.3-1: 1.
preferably, the solid content of the catalyst layer slurry is 5 to 10%.
The prepared fresh catalyst layer slurry can be directly used for preparing the catalytic membrane electrode, and can also be stored for 3-4 days at 0-20 ℃ for use.
A catalytic membrane electrode comprises the catalyst layer, wherein the catalyst layer is prepared in a form of slurry and sprayed on the catalytic membrane electrode, and specifically, the slurry is prepared in the two preferable modes.
Preferably, the catalyst layer comprises a cathode catalyst layer and an anode catalyst layer, and the noble metal loading of the cathode catalyst layer is 0.1 +/-0.02 mg/cm2The noble metal loading of the anode catalyst layer is 0.25 +/-0.02 mg/cm2。
Respectively and directly coating anode and cathode catalyst layers on two sides of a commercial Proton Exchange Membrane (PEM) by the catalyst layer slurry through an ultrasonic sprayer to prepare a catalytic membrane electrode; the PEM is a perfluorosulfonic acid ion exchange membrane, the catalyst slurry is ultrasonically sprayed and deposited on the proton exchange membrane layer by layer under stirring, and the catalytic membrane electrode (CCM) is finally prepared by drying and hot pressing.
Compared with the prior art, the invention has the beneficial effects that:
the polyamide-amine dendrimer is used as a template agent, the nano structure, the particle size and the distribution of the catalyst can be better controlled at the atom and molecule levels, and the utilization rate of noble metal can be greatly improved, so that the performance of the fuel cell is improved, and the cost is reduced.
The surface functionalized conductive carbon black and PGM-DENC are covalently cross-linked through amide to form PGM (C) -DENC, so that the conductivity of the catalyst is improved.
The catalyst slurry prepared by the slurry preparation process has good stability and fluidity.
Description of the drawings:
FIG. 1 is a synthesis scheme of PGM-DENC;
FIG. 2 is a synthesis scheme of modification of conductive carbon black particles and PGM (C) -DENC;
figure 3 is a graph of performance testing of single fuel cells of the catalyzed mea of examples 1-4.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
The conductive carbon Black used in the invention is Vulcan XC-72R, XC-72 (CARBOTS. USA), Black Pearls 2000 (CARBOTS. USA), acetylene Black, Ketjen Black series conductive carbon Black (Japan lion king company)
The polyamide-amine dendrimer used in the invention is the 4 th-10 th generation PAMAM;
abbreviations for reagents:
PAMAM, polyamidoamine;
PEMFCs, proton exchange membrane fuel cells;
PGM, noble metals;
PGM-DENC, a nano noble metal catalyst wrapped by polyamide-amine dendrimer;
pgm (c) -DENC, conductive carbon black coated noble metal electrocatalyst;
MES, 2- (N-morpholine) ethanesulfonic acid;
NHS, N-hydroxysuccinimide.
Example 1
(1) As shown in FIG. 1, a certain amount of Polyamidoamine (PAMAM) dendrimer (such as G5) aqueous solution (0.1-2.0 wt%) is measured, the pH of the solution is adjusted to 2-7 with dilute hydrochloric acid (such as 0.3M hydrochloric acid), and a certain amount of 0.3-0.5M K2PtCl4Adding the aqueous solution into the aqueous solution of PAMAM dendrimer, stirring the resulting mixed solution at room temperature for a sufficient time to allow Pt to form2+Fully complexed inside the PAMAM dendrimer, and then an excess of 0.3-0.5M NaBH4Adding the aqueous solution into the mixed solution at the temperature of 5-20 ℃ under stirring until the complexed metal Pt2+Is completely reduced into Pt, and finally is filtered, washed and dried (8 ℃) to prepare the PAMAM dendrimer coated nano-metal Pt catalyst, and the catalyst prepared in this way is defined as Pt-DENC. The nano catalyst wrapped by the PAMAM dendrimer synthesized by the invention can be further dispersed in deionized water by ultrasonic, and the structure and the particle size of the noble metal Pt can be further adjusted by repeating the preparation processes of complexation, reduction and the like.
(2) Preparation of surface functionalized conductive carbon black: 0.5g of conductive carbon black (the particle size is less than 300nm) is weighed and added into a concentrated nitric acid solution, the mixture is washed by deionized water and filtered after being stirred for at least 5h at room temperature, the filtered matter is dried and then transferred into 500ml of deionized water for ultrasonic dispersion, 0.5M MES buffer solution is added, then 100ml of 0.2M ethyl chloroformate solution is dropwise added into the carbon black solution which contains the buffer solution and is acidified on the surface under vigorous stirring, the mixture is stirred for 30 min, then 100ml of 0.2M NHS solution is added, and the stirring is continued for 2h, so that the esterification reaction of NHS is completed. Finally, the carbon black is separated, washed by deionized water and dried (at 80 ℃) to prepare the functionalized carbon black with esterified surface.
(3) Weighing a certain amount of surface functionalized carbon black particles, ultrasonically dispersing the surface functionalized carbon black particles in 20ml of 0.5M NHS buffer aqueous solution, adding a certain amount of Pt-DENC (the mass ratio of carbon to Pt-DENC is preferably 0.1-0.5%, for example, the mass ratio of the embodiment can be controlled to be 0.25%) into the surface functionalized carbon black-containing dispersion liquid, stirring for 1-2 hours to ensure that amidation between the surface functionalized carbon black and the Pt-DENC is complete, separating and filtering, washing with deionized water until the pH value is neutral, and drying at 50 ℃ to prepare Pt (C) -DENC.
An amount of pt (c) -DENC was weighed and ultrasonically dispersed in deionized water to wet well (DI water, 18M Ω cm) to avoid oxidation of the catalyst by the late addition of alcohol. Then, about half of the total amount of isobutanol is added dropwise into the wetted pt (c) -DENC, and after mixing uniformly, a certain amount of 10% perfluorosulfonic acid ionomer (ionimer) solution is added while stirring at a mass ratio of 0.3 to 1, for example, 0.6 in this example, to carbon in the pt (c) -DENC, and finally the remaining half of IPA is added. The catalyst slurry in example 1 has a solids content of 5-10 wt% (e.g., this example controls a solids content of 5%).
(4) The catalyst slurry prepared by the method is ultrasonically sprayed on a commercial proton exchange membrane in a layer-by-layer spraying mode under stirring, and a catalytic membrane electrode (CCM) is prepared by drying and hot pressing. The Pt loading amounts of the anode and the cathode of the catalyst layer are respectively controlled to be 0.102mg/cm2，0.242mg/cm2. The catalytic membrane electrode prepared in example 1 was designated CCM-1.
Example 2
(1) The same procedure was used to prepare Pt-DENC in example 1.
(2) The same procedure as in example 1 was followed to prepare the surface-functionalized conductive carbon black.
(3) Weighing a certain amount of nano catalyst (from step 1, Pt-DENC) wrapped by PAMAM dendrimer modified by carbon black, and ultrasonically dispersing the nano catalyst in deionized water (DI water, 18M omega cm) to ensure that the catalyst is fully wetted; then, about half of the total amount of Isobutanol (IPA) is added dropwise into the wetted catalyst, mixed well, and then, with stirring, added to the catalyst in a mass ratio to the subsequent carbon of 0.3 to 1: 1, adding a certain amount of 15% perfluorosulfonic acid ion cross-linked polymer (Ionermer) aqueous solution; measuring a certain amount of a buffer solution containing surface functionalized carbon and 0.5M NHS, adding the buffer solution into slurry containing a catalyst under violent stirring, uniformly mixing, and finally adding the rest half of IPA; stirring was continued for at least 1 hour. The carbon addition described in this example is 0.1-1 wt% of the Pt-DENC nanocatalyst mass percent, and the final catalyst slurry prepared has a solid content of 5-10 wt%.
(4) In accordance with the method of step (4) in example 1, the Pt loading amounts of the anode and cathode of the catalyst layer are 0.101mg/cm2，0.238mg/cm2。
Example 3
The catalytic membrane electrode is prepared by modifying Pt-DENC with conductive carbon black without surface functionalization.
(1) The same procedure was used to prepare Pt-DENC in example 1.
(2) Weighing a certain amount of PAMAM dendrimer stable nano metal Pt catalyst (from step 1, Pt-DENC), and ultrasonically dispersing in deionized water (DI water, 18M omega cm) to ensure that the catalyst is fully wetted; then, dropwise adding about half of Isobutanol (IPA) of the total amount into the wetted catalyst, uniformly mixing, and adding a certain amount of 15% perfluorosulfonic acid ion cross-linked polymer (Ionermer) solution according to the mass ratio of 0.03-0.1 of the Pt metal catalyst under stirring; and finally, adding the rest half of IPA, wherein the solid content of the finally prepared catalyst slurry is 5-10 wt%.
(3) The preparation method is the same as example 1, and the Pt of the anode and the cathode of the catalyst layer is supportedThe amounts were 0.105mg/cm, respectively2，0.243mg/cm2. The catalytic membrane electrode prepared in example 3 was designated as CCM-3.
Example 4
Example 4 as a comparative example a commercial Pt/C catalyst using 40 wt% Pt was used to formulate a catalyst slurry, the other slurry ingredients and formulation procedures were the same as in example 1; the catalytic membrane electrode (CCM) preparation process was the same as in example 1, and the catalytic membrane electrode prepared from a commercial catalyst was named CCM-4, and the Pt loadings of the anode and cathode of the catalyst layer were 0.101mg/cm2，0.254mg/cm2。
The catalytic membrane electrode (CCM1-4) gas diffusion layer prepared by examples 1-4 was assembled to a cell active area of 25cm using a commercial carbon paper with a microporous carbon layer supported on one side2After a single fuel cell, the test was carried out under the following test conditions:
fuel (H)2Anode) and Air (Air, cathode) stoichiometry: 1.2H22.0Air, humidification temperature 75 ℃, cell operation temperature 75 ℃, relative humidity 100 RH%, cell back pressure fixed at 1 atm.
The electrochemical active specific surface (ECSA) of the catalytic membrane electrode is obtained by adopting a cyclic voltammetry technology, an anode is used as a reference electrode and a counter electrode, the cathode voltage is scanned from 0.06V to 1.15V, and the scanning rate is 20 mV/s.
Table 1 performance test data for single fuel cells with catalytic membrane electrode as the component
Figure BDA0002509765450000091
As can be seen from table 1, the catalytic membrane electrodes prepared in examples 1 and 2 by using the method of the present invention are different only in the process of preparing the catalytic layer slurry, and the maximum power density is significantly improved in examples 1 and 2 compared to the comparative example, which indicates that the use ratio of the noble metal can be improved when the synthesized nano noble metal catalyst is applied to the proton exchange membrane fuel cell by using the polyamide-amine dendrimer as the template and the stabilizer, and further, the conductivity of the catalyst is improved by modifying the nano catalyst with the surface functionalized conductive carbon black.
Example 3 differs from example 2 only in that the polyamidoamine dendrimer precious metal nanocatalyst of example 3 is not modified with surface functionalized conductive carbon black, thus resulting in a significant reduction of the maximum power density of the catalytic membrane electrode prepared therefrom.
Compared with the example 2, the difference of the comparative example is only that the commercial Pt/C catalyst is adopted in the comparative example, while the polyamide-amine dendrimer is adopted in the example 2 to coat the nano noble metal catalyst and carry out the modification of the conductive carbon black, the maximum power density of the comparative example is obviously reduced compared with the invention.
The invention provides a technology for synthesizing a nano noble metal electrocatalyst and a catalyst layer preparation technology by using polyamide-amine dendrimer as a template agent and a stabilizer, thereby preparing a catalytic membrane electrode (CCM) with high performance and low platinum. Compared with the prior art and products, the preparation process of the catalytic membrane electrode adopted by the invention is simple and environment-friendly. The invention applies the technology of controllable and adjustable nanometer structure and grain diameter (PAMAM tree-shaped molecular template technology) to the preparation of the catalytic membrane electrode and the catalyst layer thereof for the first time, thereby obtaining the catalytic membrane electrode and the Membrane Electrode Assembly (MEA) thereof and obviously improving the performance of the fuel cell. As shown in FIG. 3, comparing CCM-4 obtained from the commercial catalysts of example 1(CCM-1) and the comparative example, the catalytic membrane electrode prepared according to the present invention exhibits higher power density, which is significantly advantageous over the current commercial catalytic membrane electrode, and has noble metal content: (C)<0.35mg/cm2) Lower (the dosage of the noble metal of the commercial membrane electrode is 0.4-0.6mg/cm generally2) (ii) a The electrochemical performance results of comparative examples 1(CCM-1) and 3(CCM-3) reveal the importance of the conductive carbon black to the surface modification of the nano electrocatalyst, which was first proposed by the present invention and is listed in the test data of electrochemical performance in Table 1, further confirming that the catalyst membrane electrode technology prepared by the present invention is superior to the current commercial product (CCM-4).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A catalyst layer comprises a nano noble metal catalyst and conductive carbon black, and is characterized in that the mass ratio of the conductive carbon black to the nano noble metal catalyst is 0.01% -1%, the nano noble metal catalyst is a nano noble metal catalyst wrapped by polyamide-amine dendrimer, and the conductive carbon black is prepared in the following way: adding conductive carbon black into an acid solution for acidification treatment, then carrying out esterification or anhydride modification on the conductive carbon black, separating, washing and filtering, and drying the obtained filtrate to obtain the surface functionalized conductive carbon black.
2. A method for preparing slurry is characterized by comprising the following steps: adding a polyamide-amine dendrimer coated nano noble metal catalyst and surface functionalized conductive carbon black into an N-hydroxysuccinimide aqueous solution, stirring for reaction to obtain a carbon-modified polyamide-amine dendrimer coated nano noble metal catalyst, performing ultrasonic dispersion in deionized water, then dropwise adding the carbon-modified polyamide-amine dendrimer coated nano noble metal catalyst into the deionized water according to the sequence of firstly preparing an isobutanol solvent, then preparing an ionomer aqueous solution, and finally supplementing the isobutanol solvent, and stirring for reaction to obtain a catalyst layer slurry; surface functionalization is the anhydrization or esterification of the surface of the conductive carbon black.
3. A method for preparing slurry is characterized by comprising the following steps: ultrasonically dispersing a polyamide-amine dendrimer coated nano noble metal catalyst in deionized water, then adding the deionized water according to the sequence of firstly adding an isobutanol solvent and then an aqueous solution of an ionomer into the deionized water, uniformly stirring, adding an N-hydroxysuccinimide aqueous solution containing surface functionalized conductive carbon black, then supplementing and adding the isobutanol solvent, and stirring to obtain catalyst layer slurry; surface functionalization is the anhydrization or esterification of the surface of the conductive carbon black.
4. The method for producing slurry according to claim 2 or 3, wherein the mass ratio of the ionomer to the surface-functionalized conductive carbon black particles is from 0.3 to 1: 1.
5. the method of producing a slurry according to claim 2 or 3, characterized in that the solid content of the catalyst layer slurry is 5 to 10%.
6. A catalytic membrane electrode comprising the catalyst layer of claim 1.
7. The catalyzed membrane electrode of claim 6, wherein the catalyst layer comprises a cathode catalyst layer and an anode catalyst layer, the cathode catalyst layer having a precious metal loading of 0.1 ± 0.02mg/cm2The noble metal loading of the anode catalyst layer is 0.25 +/-0.02 mg/cm2。
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