CN110504472B - Direct methanol fuel cell membrane electrode for improving catalyst utilization rate and preparation method thereof - Google Patents
Direct methanol fuel cell membrane electrode for improving catalyst utilization rate and preparation method thereof Download PDFInfo
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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
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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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
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
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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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
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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
- 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]
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- 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
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- 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 discloses a direct methanol fuel cell membrane electrode capable of improving the utilization rate of a catalyst and a preparation method thereof, relating to the technical field of fuel cells. The double-microporous-layer structure has a high three-phase reaction interface and an electrochemical reaction area, effectively reduces the substance transmission resistance in the electrode, and powerfully improves the utilization rate of the catalyst, thereby improving the discharge performance of the electrode and prolonging the service life of the battery. Through single cell performance test, compared with the membrane electrode prepared by the traditional method, the membrane electrode prepared by the preparation method provided by the invention is obviously improved in monomer performance.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a direct methanol fuel cell membrane electrode capable of improving the utilization rate of a catalyst and a preparation method thereof.
Background
A Direct Methanol Fuel Cell (DMFC) is a power generation device that can continuously and directly convert chemical energy in fuel and oxidant into electric energy, and has attracted wide attention worldwide due to its environmental protection and high efficiency. Methanol fuel cells directly utilize methanol or aqueous methanol as the anode fuel and oxygen or air as the oxidant. The methanol reforming device has the characteristics of wide methanol source, convenience in carrying, storage and supplement, high specific energy of volume and mass, simple structure, no need of external reforming equipment and the like, and has wide application prospect in the aspects of portable power supplies, small-sized civil power supplies, vehicle power supplies and the like.
The membrane electrode is used as a core component of the direct methanol fuel cell and directly determines the performance of the cell. However, the current DMFC has a problem of low electrocatalytic activity of the methanol anode. The methanol oxidation mechanism is very complicated, unstable and insoluble intermediate products are generated in the process, and some intermediate products can be adsorbed on the surface of the catalyst, so that the activity of the catalyst is inhibited, and the catalyst is poisoned and the utilization rate of the catalyst is low. Therefore, research on optimizing the membrane electrode structure, improving the catalyst utilization rate and the electrochemical reaction area, and the like are hot spots of DMFC research.
Most of the current work has focused on modification of the catalyst support or catalytic layer structure, but the problem of degradation of the battery performance due to catalyst settling caused by assembly pressure, methanol flow, gas flow, etc. has yet to be solved. When the cell is operated for a period of time, part of the catalyst cannot react with
Ionic polymers are contacted, so that protons cannot be transferred, and a catalyst cannot work, so that the electrode has high electrochemical reaction resistance, and the performance of the battery is reduced. In view of this, we constructed a novel membrane electrode with a double microporous layer. The microporous layer consists of an inner microporous layer (with addition of Nafion polymer) and an outer microporous layer (with addition of PTFE polymer). The existence of the inner microporous layer can enlarge the three-phase interface area of the reaction and improve the utilization rate of the catalyst.
Disclosure of Invention
The invention aims to provide a direct methanol fuel cell membrane electrode for improving the utilization rate of a catalyst, thereby achieving the purposes of increasing a three-phase reaction interface and the electrochemical active area, improving the utilization rate of the catalyst, reducing the electrochemical reaction resistance and the mass transfer resistance of the electrode and improving the performance of a single cell.
The technical scheme of the invention is as follows:
a direct methanol fuel cell membrane electrode capable of improving the utilization rate of a catalyst comprises a direct methanol fuel cell membrane electrode on which a microporous layer is prepared, the microporous layer having a double-layer structure comprising an outer microporous layer containing a hydrophobic polymer and an inner microporous layer containing a polymer having proton conductivity;
a preparation method of a double microporous layer membrane electrode comprises the following steps:
the method comprises the following steps: treatment of gas diffusion layers
Soaking the gas diffusion layer in hydrophobic polymer solution with a certain concentration for 30-90 seconds, putting the gas diffusion layer into an oven for drying, and putting the gas diffusion layer into a muffle furnace for sintering after drying to obtain the gas diffusion layer with a hydrophobic surface, wherein the mass fraction of the hydrophobic polymer on the gas diffusion layer is 20-40 wt.%.
Step two: preparation of an outer microporous layer
Uniformly spraying slurry containing carbon powder and hydrophobic polymers on the surface-hydrophobic gas diffusion layer obtained in the step one), putting the carbon paper coated with the slurry into an oven for drying, and then putting the carbon paper into a muffle furnace for sintering to obtain an outer microporous layer, wherein the mass fraction of polytetrafluoroethylene in the outer microporous layer is 15-30 wt.%.
Step three: preparation of inner microporous layer
Uniformly spraying slurry of carbon powder and a polymer with proton conductivity on the surface of the outer microporous layer obtained in the step two), putting the microporous layer coated with the slurry into an oven for drying, wherein the mass fraction of the polymer with proton conductivity in the inner microporous layer is 20-40 wt%, and thus obtaining the microporous layer with a double-layer structure.
Step four: preparation of catalytic layer
Uniformly coating catalyst slurry containing a proton conductor on the microporous layer with the double-layer structure obtained in the step three), wherein the catalyst is Pt/C or PtRu/C with the weight percentage of metal of 40-70 wt%, and placing the microporous layer in an oven for a period of time after spraying until drying, so as to obtain the electrode of the direct methanol fuel cell with the improved catalyst utilization rate.
Step five: assembly of membrane electrode
And C), pressing the electrode of the direct methanol fuel cell with the improved catalyst utilization rate obtained in the step four) with a proton exchange membrane with ion conductivity under the pressing pressure of 6.0-8.0 N.m, pressing at room temperature without hot pressing, and thus obtaining the direct methanol fuel cell membrane electrode with the improved catalyst utilization rate.
Further, the time for soaking the gas diffusion layer in the hydrophobic polymer in the step one) is 30-90 seconds, the sintering temperature in the muffle furnace is 350-400 ℃, and the time is 40-60 minutes.
Further, the gas diffusion layer in the step one) is carbon paper, carbon cloth, foam nickel or other materials with electric conductivity, and surface impurities are removed.
Further, the hydrophobic polymer in the step one) is polytetrafluoroethylene, polyvinyl alcohol or polyvinylidene fluoride, and the mass fraction of the hydrophobic polymer on the gas diffusion layer is 20-40 wt.%.
Further, the slurry in the step two) is a mixed solution of carbon powder, hydrophobic polymer and dispersing solvent; wherein the mass fraction of the hydrophobic polymer in the outer microporous layer is 15-30 wt.%.
Further, the slurry in the step three) is a mixed solution of carbon powder, a polymer with proton conductivity and a dispersing solvent, wherein the volume of the dispersing solvent is 5-10 ml.
Further, in the third step), the polymer with proton conductivity is perfluorosulfonic acid-polytetrafluoroethylene, and the dispersion solvent is isopropanol, ethanol and acetone; wherein the mass fraction of the perfluorosulfonic acid-polytetrafluoroethylene in the inner microporous layer is 20-40 wt.%.
Further, the anode catalyst in the fourth step) is Pt/C or PtRu/C with the metal content of 40wt.% to 70wt.%, and the metal loading in the anode catalyst layer is 2mg cm-2-5mg cm-2(ii) a The cathode catalyst is Pt/C or PtRu/C with the metal weight percentage of 40 wt% -70 wt%, and the metal loading in the cathode catalyst layer is 1.5mg cm-2-3mg cm-2。
Further, the mass fraction of the proton conductor in the catalytic layer in the fourth step) is 25wt.% to 40 wt.%.
Further, the proton exchange membrane in the step five) is a perfluorosulfonic acid membrane, the pressing condition of the electrode of the direct methanol fuel cell and the proton exchange membrane is 6.0 N.m-8.0 N.m, and the pressing is carried out at room temperature.
(1) Treatment of gas diffusion layers
Soaking the gas diffusion layer in a polytetrafluoroethylene solution with a certain concentration for 30 seconds, putting the carbon paper into a drying oven for drying, and putting the carbon paper into a muffle furnace for sintering after drying to obtain the carbon paper with a hydrophobic surface, wherein the mass fraction of polytetrafluoroethylene on the gas diffusion layer is 20-30 wt.%.
(2) Preparation of an outer microporous layer
And (2) uniformly spraying slurry containing carbon powder and polytetrafluoroethylene on the carbon paper with the hydrophobic surface obtained in the step (1), putting the carbon paper coated with the slurry into an oven for drying, and then putting the carbon paper into a muffle furnace for sintering to obtain an outer microporous layer, wherein the mass fraction of the polytetrafluoroethylene in the outer microporous layer is 15-20 wt.%.
(3) Preparation of inner microporous layer
And (3) uniformly spraying slurry of carbon powder and perfluorosulfonic acid-polytetrafluoroethylene (Nafion) copolymer on the surface of the outer microporous layer obtained in the step (2), putting the microporous layer coated with the slurry into an oven for drying, wherein the mass fraction of Nafion in the inner microporous layer is 25-35 wt%, and thus obtaining the microporous layer with a double-layer structure.
(4) Preparation of catalytic layer
And (3) uniformly coating catalyst slurry containing a proton conductor on the microporous layer with the double-layer structure obtained in the step (3), wherein the catalyst is Pt/C or PtRu/C with the metal weight percentage of 40-70 wt%, and after spraying, placing the microporous layer in an oven for a period of time until drying, so that the electrode of the direct methanol fuel cell with the improved catalyst utilization rate is obtained.
(5) Assembly of membrane electrode
And (4) pressing the electrode of the direct methanol fuel cell with the improved catalyst utilization rate obtained in the step (4) with a proton exchange membrane with ion conductivity under the pressing pressure of 7.5 N.m, and pressing at room temperature without hot pressing to obtain the direct methanol fuel cell membrane electrode with the improved catalyst utilization rate.
Compared with the traditional membrane electrode with a single microporous layer, the membrane electrode with the double microporous layers provided by the invention has the following advantages:
(1) greater electrochemically active area
When the cell is operated for a period of time, a part of the catalyst sinks into the microporous layer due to the influence of the assembly pressure, the methanol feed and the gas flow, and the conventional electrode mono-microporous layer does not contain a proton conductor in the structure, so that the part of the catalyst is not utilized, and the three-phase reaction interface is reduced. In the double-microporous-layer electrode provided by the invention, the proton conductor is added in the inner microporous layer, so that the catalyst is utilized, and the electrochemical active area is enlarged.
(2) Higher catalyst utilization
The inner microporous layer of the invention enables the part of the catalyst leaked into the microporous layer to be utilized, and improves the utilization rate of the catalyst, thereby greatly reducing the preparation cost of the electrode.
(3) Lower mass transfer resistance
The conventional electrode single microporous layer is usually of a hydrophobic structure, which causes the difficulty in feeding methanol at low concentration, increases the mass transfer resistance in the electrode and influences the performance of a single cell. The Nafion polymer is added in the double-micropore layer, so that the double-micropore layer has high hydrophilicity, the transmission of methanol is enhanced, and the mass transfer resistance of an electrode is reduced.
Drawings
FIG. 1 is a schematic diagram of a membrane electrode structure of a direct methanol fuel cell according to the present invention for improving the utilization rate of a catalyst;
FIG. 2 is a flow chart of a direct methanol fuel cell electrode preparation process for improving catalyst utilization according to the present invention;
FIG. 3 is a flow chart of the membrane electrode assembly process for improving the catalyst utilization of the DMFC according to the present invention;
FIG. 4 is a graph of the discharge performance of the fuel cell of example 1;
FIG. 5 is a graph of the discharge performance of the fuel cell of example 2;
FIG. 6 is a graph of the discharge performance of the fuel cell of example 3;
FIG. 7 is a graph of the discharge performance of the fuel cell of example 4;
FIG. 8 is a graph of discharge performance of a fuel cell of comparative example 1;
FIG. 9 is a graph of discharge performance of a fuel cell of comparative example 2;
FIG. 10 is a graph of discharge performance of a fuel cell of comparative example 3;
fig. 11 is a graph of discharge performance of the fuel cell of comparative example 4.
The reference numbers are as follows:
1-a gas diffusion layer; 2-a microporous layer comprising PTFE; 3-a microporous layer comprising Nafion; 4-anode catalyst layer; 5-a proton exchange membrane; 6-cathode catalyst layer.
Detailed Description
Example 1
Preparing direct methanol fuel cell electrode and membrane electrode with improved catalyst utilization rate according to the flow and process shown in figure 2, and performing discharge test, mainly comprising the following steps:
(1) preparation of the electrodes
A microporous layer 2 containing Polytetrafluoroethylene (PTFE) with a polytetrafluoroethylene content of 15wt.% was applied on the hydrophobic diffusion layer, using a PTFE-containing carbon paper as the diffusion layer. On the outer microporous layer, a microporous layer 3 containing Nafion was coated, wherein the Nafion content was 30 wt.%. Catalyst slurry was prepared in an appropriate ratio, and isopropanol was used as a solvent. A catalyst slurry was sprayed on the Nafion-containing microporous layer 3 using Pt Ru/C as a catalyst on the anode side and Pt/C as a catalyst on the cathode side to form a catalyst layer.
(2) Treatment of proton exchange membranes
The membrane was at 5wt.% H2O2The solution was boiled for 1 hour, then rinsed in deionized water, then boiled in 0.5M sulfuric acid solution for 1 hour, and finally boiled in deionized water for 1 hour. The pre-treated membrane was stored in deionized water prior to pressing the MEA.
(3) Membrane electrode assembly
And (3) pressing two electrodes with a double-microporous-layer structure with a Nafion 212 membrane under the pressing condition of 7.5 N.m at room temperature without hot pressing to obtain the direct methanol fuel cell membrane electrode with the improved catalyst utilization rate.
(4) Test of discharge Performance
And testing the membrane electrode assembly and the sealing air cushion after assembling in a single cell, wherein the testing conditions are as follows: the working temperature of the cell is 60 ℃, the pressure is normal, the anode fuel is 0.5M methanol (the flow is 3ml min)-1) The cathode inlet air is dry oxygen (the flow rate is 199ml min)-1). The limiting current density can reach 120.17mA cm-2The maximum power density reaches 22.23mW cm-2The maximum power density of example 1 was increased by 56.53% compared to comparative example 1.
Example 2
The direct methanol fuel cell membrane electrode with the catalyst utilization rate is tested under the conditions of high-concentration methanol and dry oxygen. First, a dual microporous layer electrode was prepared according to the same procedure as in example 1.
And testing the membrane electrode assembly and the sealing air cushion after assembling in a single cell, wherein the testing conditions are as follows: the working temperature of the cell is 60 ℃, the pressure is normal, the anode fuel is 2M methanol (the flow is 3ml min)-1) The cathode inlet air is dry oxygen (the flow rate is 199ml min)-1). The limiting current density can reach 500.21mA cm-2The maximum power density reaches 76.29mW cm-2Example 2 is an improvement of 41.01% over comparative example 2.
Example 3
The direct methanol fuel cell membrane electrode with the catalyst utilization rate is tested under the conditions of low-concentration methanol and humidified oxygen. First, a dual microporous layer electrode was prepared according to the same procedure as in example 1.
And testing the membrane electrode assembly and the sealing air cushion after assembling in a single cell, wherein the testing conditions are as follows: the working temperature of the cell is 60 ℃, the pressure is normal, the anode fuel is 0.5M methanol (the flow is 3ml min)-1) The cathode inlet gas is humidified oxygen (relative humidity is 60%, and flow is 199ml min)-1). The limiting current density can reach 135.05mA cm-2The maximum power density reaches 29.12mW cm-2Example 3 is a 97.38% improvement over comparative example 3.
Example 4
The direct methanol fuel cell membrane electrode with the catalyst utilization rate is tested under the conditions of high-concentration methanol and humidified oxygen. First, a dual microporous layer electrode was prepared according to the same procedure as in example 1.
And testing the membrane electrode assembly and the sealing air cushion after assembling in a single cell, wherein the testing conditions are as follows: the working temperature of the cell is 60 ℃, the pressure is normal, the anode fuel is 2M methanol (the flow is 3ml min)-1) The cathode inlet gas is humidified oxygen (relative humidity is 60%, and flow is 199ml min)-1). The limiting current density can reach 550.12mA cm-2The maximum power density reaches 81.04mW cm-2Example 4 is an improvement of 36.65% over comparative example 4.
Comparative example 1
And preparing a fuel cell electrode with a conventional microporous layer structure and a membrane electrode for comparing the discharge performance. The method comprises the following steps:
(1) preparing a membrane electrode: a carbon paper containing Polytetrafluoroethylene (PTFE) was used as the anode diffusion layer. An outer microporous layer was coated on the hydrophobic diffusion layer with a polytetrafluoroethylene content of 15 wt.%. An appropriate amount of catalyst was dispersed in deionized water, isopropanol, and Nafion solution to prepare a catalyst slurry. Pt Ru/C was used as a catalyst on the anode side and Pt/C was used as a catalyst on the cathode side. And coating the catalyst slurry on the microporous layer to form a catalyst layer. The Nafion 212 membrane is pretreated to remove organic and inorganic contaminants. The pretreatment process included subjecting the membrane to 5 wt% H2O2The solution was boiled for 1 hour, then washed in deionized water, then boiled in 0.5M sulfuric acid solution for 1 hour, and finally boiled in deionized water for 1 hour. The pre-treated membrane was stored in deionized water prior to assembly of the MEA.
(2) Assembling a membrane electrode: the electrolyte membrane is a Nafion 212 membrane, two prepared same gas diffusion electrodes are placed on two sides of the electrolyte membrane and are pressed by using the assembly pressure of 7.5 N.m, and the membrane electrode three-in-one component is obtained.
(3) Single cell testing: the membrane electrode three-in-one component and the sealing air cushion are assembled in a single cellThe test conditions were the same as in example 1. The limiting current density reaches 99.98mA cm-2The maximum power density reaches 14.20mW cm-2。
Comparative example 2
The discharge performance of the fuel cell electrode and the membrane electrode with the conventional microporous layer structure are compared under the conditions of high-concentration methanol and dry oxygen.
First, a fuel cell electrode and a membrane electrode of a conventional microporous layer structure were prepared and assembled by the same procedure as in comparative example 1. The resulting three-in-one membrane electrode assembly and the sealing air cushion were assembled in a single cell and tested under the same conditions as in example 2. The limiting current density reaches 350.07mA cm-2The maximum power density reaches 54.11mW cm-2。
Comparative example 3
The discharge performance comparison of the fuel cell electrode and the membrane electrode with the conventional microporous layer structure is carried out under the conditions of low-concentration methanol and humidified oxygen.
First, a fuel cell electrode and a membrane electrode of a conventional microporous layer structure were prepared and assembled by the same procedure as in comparative example 1. The resulting three-in-one membrane electrode assembly and the sealing air cushion were assembled in a single cell and tested under the same conditions as in example 3. The limiting current density reaches 82.34mA cm-2The maximum power density reaches 14.75mW cm-2。
Comparative example 4
The discharge performance comparison of the fuel cell electrode and the membrane electrode with the conventional microporous layer structure is carried out under the conditions of low-concentration methanol and humidified oxygen.
First, a fuel cell electrode and a membrane electrode of a conventional microporous layer structure were prepared and assembled by the same procedure as in comparative example 1. The resulting three-in-one membrane electrode assembly and the sealing air cushion were assembled in a single cell and tested under the same conditions as in example 4. The limiting current density reaches 375.04mA cm-2The maximum power density reaches 59.30mW cm-2。
As can be seen from the comparative examples, the direct methanol fuel cell electrode and the membrane electrode according to the present invention, which improve the catalyst utilization, have better discharge performance. When the temperature is 60 ℃, the maximum discharge current density and the maximum power density of the embodiment are greatly improved compared with the comparative example no matter the embodiment is wet or dry, and the maximum power density of the embodiment 1 is improved by 56.53 percent compared with the comparative example 1; example 2 is an improvement of 41.01% over comparative example 2; example 3 is increased by 97.38% compared to comparative example 3; example 4 is an improvement of 36.65% over comparative example 4. The addition of the inner microporous layer is illustrated to make use of the catalyst which is not available and partially seeps down to the microporous layer due to the operation of the battery, thus improving the utilization rate of the catalyst. The double-microporous-layer structure increases the electrochemical active area of the battery, reduces mass transfer resistance, and plays a role in promoting electrochemical reaction efficiency and mass transfer, so that the discharge performance of the battery is effectively improved.
It should be noted that, according to the embodiments of the present invention, those skilled in the art can fully implement the full scope of the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a partial embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.
Claims (5)
1. A preparation method of a direct methanol fuel cell membrane electrode for improving the utilization rate of a catalyst comprises a gas diffusion layer, a microporous layer, a catalyst layer and a proton exchange membrane, and is characterized in that the microporous layer of the direct methanol fuel cell membrane electrode has a double-layer structure and comprises an outer microporous layer containing a hydrophobic polymer and an inner microporous layer containing a polymer with proton conductivity; also comprises the following steps:
the method comprises the following steps: soaking the gas diffusion layer in solution of hydrophobic polymer with certain concentration for a period of time, drying the gas diffusion layer in a drying oven, and sintering the gas diffusion layer in a muffle furnace after drying to obtain the gas diffusion layer with hydrophobic surface; wherein the time for soaking the gas diffusion layer in the hydrophobic polymer is 30-90 seconds, the sintering temperature in a muffle furnace is 350-400 ℃, and the time is 40-60 minutes;
step two: preparation of outer microporous layer: uniformly spraying slurry containing carbon powder and hydrophobic polymers on the surface-hydrophobic gas diffusion layer obtained in the step one), putting the gas diffusion layer coated with the slurry into an oven for drying, and then putting the gas diffusion layer into a muffle furnace for sintering to obtain an outer microporous layer;
step three: preparation of inner microporous layer: uniformly spraying slurry of carbon powder and a polymer with proton conductivity on the surface of the outer microporous layer obtained in the step two), and putting the microporous layer coated with the slurry into an oven for drying to obtain a microporous layer with a double-layer structure;
step four: preparation of the catalytic layer: uniformly coating catalyst slurry containing proton conductors on the microporous layer with the double-layer structure obtained in the step three), and putting the microporous layer into an oven to be kept for a period of time until the microporous layer is dried, so as to obtain the electrode of the direct methanol fuel cell for improving the utilization rate of the catalyst;
step five: assembling a membrane electrode: pressing the electrode of the direct methanol fuel cell with the improved catalyst utilization rate obtained in the step four) with a proton exchange membrane with ion conductivity to obtain a direct methanol fuel cell membrane electrode with the improved catalyst utilization rate;
the hydrophobic polymer in the first step) is polytetrafluoroethylene, polyvinyl alcohol or polyvinylidene fluoride, and the mass fraction of the hydrophobic polymer on the gas diffusion layer is 20-40 wt%;
the anode catalyst in the step four) is Pt/C or PtRu/C with the weight percentage of metal of 40-70 wt.%, and the metal loading in the anode catalyst layer is 2 mg-cm-2-5mg·cm-2(ii) a The cathode catalyst is P/C or PtRu/C with the metal weight percentage of 40-70 wt.%, and the metal loading in the cathode catalyst layer is 1.5 mg-cm-2-3mg·cm-2；
The mass fraction of the proton conductor in the catalytic layer in the step four) is 25-40 wt%;
and fifthly), pressing the proton exchange membrane which is a perfluorosulfonic acid membrane at room temperature under the condition that the pressure of an electrode of the direct methanol fuel cell and the proton exchange membrane is 6.0-8.0 Nm.
2. The method for preparing a membrane electrode assembly for a direct methanol fuel cell with improved catalyst utilization rate as claimed in claim 1, wherein the gas diffusion layer in the step one) is carbon paper, carbon cloth, nickel foam or other materials with conductivity which are subjected to surface impurity removal.
3. The method for preparing a direct methanol fuel cell membrane electrode for improving the catalyst utilization rate according to claim 1, wherein the slurry component in the step two) is a mixed solution of carbon powder, hydrophobic polymer and dispersing solvent; wherein the mass fraction of the hydrophobic polymer in the outer microporous layer is 15-30 wt.%.
4. The method for preparing a direct methanol fuel cell membrane electrode for improving the catalyst utilization rate according to claim 1, wherein the slurry component in the step three) is a mixed solution of carbon powder, a polymer with proton conductivity and a dispersion solvent, wherein the volume of the dispersion solvent is 5-10 ml.
5. The method for preparing a direct methanol fuel cell membrane electrode for improving the catalyst utilization rate according to claim 4, wherein the polymer with proton conductivity in the third step) is perfluorosulfonic acid-polytetrafluoroethylene, and the dispersion solvent is isopropanol, ethanol or acetone; wherein the mass fraction of perfluorosulfonic acid-polytetrafluoroethylene in the inner microporous layer is 20wt.% to 40 wt.%.
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| CN111916765B (en) * | 2020-07-29 | 2022-02-11 | 一汽解放汽车有限公司 | Method for preparing gas diffusion layer in fuel cell |
| CN112382767B (en) * | 2020-10-26 | 2021-10-12 | 江苏大学 | Fuel cell electrode in-situ preparation method based on double-layer ordered structure microporous layer |
| CN112331858B (en) * | 2020-10-30 | 2022-06-21 | 江苏大学 | Fuel cell electrode with catalyst in-situ grown on ordered structure microporous layer and preparation method of membrane electrode |
| CN112820883B (en) * | 2020-12-31 | 2022-03-08 | 武汉理工氢电科技有限公司 | Microporous layer slurry, gas diffusion layer, fuel cell and preparation method |
| CN113555568A (en) * | 2021-07-26 | 2021-10-26 | 中汽创智科技有限公司 | Membrane electrode and preparation method thereof |
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| CN110504472A (en) | 2019-11-26 |
| AU2020101412A4 (en) | 2020-09-10 |
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