CN113437338B - Fuel cell membrane electrode and preparation method thereof - Google Patents
Fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- CN113437338B CN113437338B CN202110742280.3A CN202110742280A CN113437338B CN 113437338 B CN113437338 B CN 113437338B CN 202110742280 A CN202110742280 A CN 202110742280A CN 113437338 B CN113437338 B CN 113437338B
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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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- 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
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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 provides a fuel cell membrane electrode and a preparation method thereof, comprising the following steps: s1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane; step S2, coating catalyst slurry on one side or two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane prepared in the step S1 to obtain a catalyst coating membrane; s3, spraying phosphoric acid on the surfaces of the catalytic layer and/or the gas diffusion layer; and S4, placing gas diffusion layers on two sides of the catalyst coating membrane obtained in the S2 to assemble the membrane electrode of the fuel cell. The method prepares the membrane electrode based on the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and the catalyst coating technology, optimizes the membrane electrode preparation technology, can improve the interface contact between a catalyst layer in the membrane electrode and the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane, reduces the interface resistance, and thus improves the electrical output performance of the membrane electrode.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a fuel cell membrane electrode and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) have the advantages of high energy conversion efficiency, no pollution, low noise, etc. The typical operating temperature of a conventional proton exchange membrane fuel cell (LT-PEMFC) is between 25 and 85 ℃, and a low operating temperature has the advantage of fast start-up, but has the outstanding problems that the fuel cell system has difficulty in dissipating heat, so that it requires a complicated cooling system, and a heat sink is bulky. In contrast, a high temperature proton exchange membrane fuel cell (HT-PEMFC) operating at 100-250 ℃ has the following advantages: (1) the working temperature is increased, the temperature difference between the fuel cell and the environment can be increased, the heat dissipation capacity of the system is improved, the cooling system is simplified, and the utilization rate of waste heat can be increased, so that the power generation efficiency of the system is improved; (2) the electrochemical reaction rate of the catalyst is improved, the use amount of the Pt catalyst is reduced, and the utilization of non-noble metal catalysts except Pt becomes possible, so that the cost of the fuel cell is greatly reduced; (3) flooding is not easy to occur, and the oxygen mass transfer capacity of the cathode is greatly improved under high current density; (4) the Pt catalyst has obviously improved carbon monoxide poisoning resistance, can use non-high-purity hydrogen, and reduces the hydrogen cost.
Currently, polybenzimidazole (PBI) is doped with phosphoric acid (H) 3 PO 4 ) High temperature proton exchange membranes are the most widely studied and have been commercially used in HT-PEMFCs. For the PBI doped phosphoric acid high-temperature proton exchange membrane, the proton conductor is phosphoric acid which is liquid from room temperature to working temperature (180 ℃), and particularly, the liquid phosphoric acid is easy to run off at low temperature; moreover, the swelling ratio is as high as 200-300%, and the mechanical strength is remarkably reduced. Chinese patent CN107331883A discloses Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and fuel cell, wherein the doped molten proton conductor (CsH) 5 (PO 4 ) 2 、KH 5 (PO 4 ) 2 ) The liquid phase is a solid at room temperature, and is transformed into a liquid melt at a temperature higher than the melting point, wherein the melt has high proton conductivity, and is not easy to run off because the liquid phase is a solid below the melting point; the PBI doped molten proton conductor electrolyte membrane has low swelling rate and can maintain good mechanical strength.
The membrane electrode is the most central component of a fuel cell as a site for electrochemical reaction in the fuel cell. The structural design and preparation process of the membrane electrode affect the characteristics of the membrane electrode, and the characteristics of the membrane electrode directly determine the overall performance of the fuel cell. Conventional membrane electrode preparation methods are conventionally classified into two types according to the difference of a catalyst layer support substrate in the membrane electrode preparation process: the CCS method in which a catalyst is coated on a gas diffusion layer substrate and the CCM method in which a catalyst is coated on a proton exchange membrane. For the membrane electrode prepared by the CCS method, the interface contact between the catalyst layer and the electrolyte membrane is not tight, the interface resistance is larger, and the output power density of the fuel cell is lower. Compared with the CCS method, the CCM method can effectively improve the utilization rate of the catalyst and reduce the interface resistance between the proton exchange membrane and the catalyst layer, thereby obtaining high output power density, and becoming the mainstream technology for preparing the membrane electrode of the LT-PEMFC at present.
For PBI doped phosphoric acid high-temperature proton exchange membrane, after PBI is doped with phosphoric acid, the swelling rate is up to 200-300%, the mechanical property is obviously reduced, and if the PBI doped phosphoric acid high-temperature proton exchange membrane is adoptedThe membrane electrode prepared by CCM method is easy to peel off the catalyst layer due to excessive swelling, so the membrane electrode prepared by CCS method in this field is conventional, including the membrane electrode of Advent company. For PBI-doped molten proton conductor electrolyte membrane, the publication (A proton conductor based on molten CsH) 5 (PO 4 ) 2 for intermediate-temperature fuel cells, RSC adv.,2018,8, 5225-5232) and Chinese patent CN107331883A (an intermediate-temperature proton exchange membrane and a preparation method thereof) adopt a CCS method to prepare a membrane electrode, and are provided with fuel cells, and the peak power density is 120mW/cm respectively under the condition of supplying hydrogen/oxygen at 200 DEG C 2 And less than 70mW/cm 2 And exhibits low electrical output performance. In order to promote the application of fuel cells based on PBI doped molten proton conductor electrolyte membranes, it is highly desirable to improve the membrane electrode and increase its output power density.
Disclosure of Invention
The invention provides a fuel cell membrane electrode and a preparation method thereof, aiming at the problems that the interface contact of a CCS type membrane electrode is poor, the interface resistance is large and the output performance of a fuel cell is low in the prior art of the membrane electrode based on a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane. The method comprises the steps of directly coating catalyst slurry on a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane to prepare a catalyst coating membrane, and then combining the catalyst coating membrane with a gas diffusion layer to obtain the membrane electrode. The Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane used by the method has good mechanical properties and dimensional stability. And the membrane electrode is prepared based on the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and the catalyst coating technology, so that the membrane electrode preparation technology is optimized, the interface contact between a catalyst layer in the membrane electrode and the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane can be improved, the interface resistance is reduced, and the electrical output performance of the membrane electrode is improved.
The invention is realized by the following scheme:
a first aspect of the present invention provides a fuel cell membrane electrode comprising a catalyst coated membrane and a gas diffusion layer disposed on both sides of the catalyst coated membrane, the catalyst coated membrane comprising a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and a catalytic layer coated on one or both sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane. Wherein the catalytic layer and/or the gas diffusion layer surface contains phosphoric acid.
Preferably, phosphoric acid is sprayed on the surface of the catalytic layer and/or the gas diffusion layer, and the content of the phosphoric acid is 1-20mg/cm 2 。
The second aspect of the present invention provides a method for preparing a fuel cell membrane electrode, comprising the steps of:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane;
s2, directly coating catalyst slurry on one side or two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane prepared in the step S1 to form a catalyst layer, and drying to obtain a catalyst coating membrane; the drying temperature is 60-200 ℃.
Step S3, coating phosphoric acid on one surface, which is attached to the catalyst coating film, on the catalyst layer and/or the gas diffusion layer;
and S4, placing gas diffusion layers on two sides of the catalyst coated membrane to assemble the fuel cell membrane electrode.
Preferably, in step S1, the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane is prepared as follows:
1) Putting the solid proton conductor in a high-temperature oven to convert the solid proton conductor into a molten proton conductor;
2) And soaking the polybenzimidazole membrane in a molten proton conductor, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane.
Preferably, the solid proton conductor is CsH 5 (PO 4 ) 2 Or KH 5 (PO 4 ) 2 。
Preferably, the soaking time of the polybenzimidazole membrane in a molten proton conductor is 6-72h.
Preferably, in step S2, the catalyst slurry comprises a mixture of a binder, a catalyst and a solvent, wherein the binder is one or more of PBI, PTFE, PVDF and PVF, the solvent is one or more of ethanol, isopropanol, n-propanol and n-butanol, and the catalyst is a platinum-on-carbon electrocatalyst, wherein the mass ratio of platinum to carbon support is (1-9): (9-1). The mixing mode of the catalyst slurry is ultrasonic, ball milling or stirring.
Preferably, in step S2, the catalyst slurry is coated by spraying, knife coating or slot extrusion coating.
Preferably, in step S3, the phosphoric acid is coated by spraying phosphoric acid on the catalytic layer and/or the gas diffusion layer, wherein the phosphoric acid content is 1-20mg/cm 2 。
Compared with the prior art, the invention has the following beneficial effects:
1. the electrolyte membrane is prepared by impregnating polybenzimidazole with a molten proton conductor, and has good mechanical properties, dimensional stability and proton conductivity.
2. The catalyst is directly coated on the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane to prepare the catalyst coating membrane, so that good interface contact between the electrolyte membrane and a catalytic layer can be ensured, the interface resistance and the material transmission resistance of the membrane electrode are reduced, and the electrical output performance is improved; moreover, partial catalyst can be prevented from being buried in the microporous layer in the preparation process of the gas diffusion electrode, so that the utilization efficiency of the catalyst can be improved;
3. coating a minute amount (1-20 mg/cm) on the catalytic layer and/or the gas diffusion layer 2 ) The phosphoric acid can improve proton transmission channels in the catalyst layer, reduce proton transmission resistance in the catalyst layer and improve the electric output performance of the membrane electrode.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of the steps for preparing a membrane electrode assembly for a fuel cell in accordance with the present invention;
FIG. 2 is a schematic structural view of a fuel cell membrane electrode assembly according to the present invention;
the electrolyte membrane comprises a gas diffusion layer 1, a gas diffusion layer 2, a catalyst coating film 21, a catalyst layer 22 and a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the invention.
The invention provides a fuel cell membrane electrode and a preparation method thereof, comprising the following steps: taking a piece of Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane, directly coating catalyst slurry on one side or two sides of the electrolyte membrane, drying to obtain a catalyst coating membrane, and combining the catalyst coating membrane with a gas diffusion layer. The method directly coats the catalyst slurry on the membrane substrate impregnated with the proton conductor, so that the utilization rate of the catalyst can be improved, the three-phase interface of the membrane electrode is optimized, and the transmission resistance of interface substances is reduced, thereby improving the electrical output performance of the membrane electrode. The method comprises the following specific steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22;
step S2, directly coating catalyst slurry on one side or both sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22 prepared in step S1 to form a catalyst layer 21, and drying to obtain a catalyst coating membrane 2; the drying temperature is 60-200 ℃.
Step S3, coating phosphoric acid on the surface of the catalytic layer 21 and/or the gas diffusion layer 1;
and S4, placing the gas diffusion layers 1 on two sides of the catalyst coating membrane 2 to assemble the fuel cell membrane electrode.
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1
The structure of the membrane electrode of the fuel cell related to the present embodiment is shown in fig. 2, and the membrane electrode comprises, from bottom to top, a gas diffusion electrode 1, a catalyst coating membrane 2 and a gas diffusion electrode 1; the catalyst coated membrane 2 includes a catalytic layer 21 and a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell in this embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 5mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 2
The structure of a fuel cell membrane electrode according to this embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 1mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 3
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the area is 3X 3cm 2 PBI membrane is soaked in molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 3mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 4
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the area is 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (3) soaking for 48 hours at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21 so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, using a spray gun to spray the phosphoric acid ethanol solution (concentrated phosphoric acid: ethanol)Volume ratio of =1: 4) Spraying the phosphoric acid solution on the catalyst layer 21, and controlling the spraying amount of the phosphoric acid to be 10mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 5
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell in this embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 PBI membrane is soaked in molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 15mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 6
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, mixing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 7
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell in this embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 Soaking for 6h at 160 deg.C, taking out polybenzimidazole membrane, removing proton conductor on membrane surface to obtain Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane,the thickness was 40 μm.
Step S2, preparing a catalyst coating film: 1) Firstly, mixing a carbon-supported platinum electrocatalyst with platinum content of 50%, a PVDF binder, deionized water and n-propanol in a mass ratio of 1:0.4:5:5: ultrasonically stirring the components together to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using a scraper coating device to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an isopropyl alcohol solution of phosphoric acid (concentrated phosphoric acid: isopropyl alcohol volume ratio =1 = 4) onto the catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 5mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the gas diffusion layers 1 are placed on both sides of the catalyst coated membrane 2 to assemble a membrane electrode assembly, and the membrane electrode assembly is pressed using a press.
Example 8
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell in this embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the area is 3X 3cm 2 PBI membrane is soaked in molten CsH 5 (PO 4 ) 2 And (3) taking out the polybenzimidazole membrane after the soaking time is finished for 72h at the soaking temperature of 160 ℃, and removing the proton conductor on the surface of the membrane to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PBI (Poly-p-phenylene Benzene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using slit coating equipment to form a catalyst layer 21 so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an n-propanol solution of phosphoric acid (concentrated phosphoric acid: n-propanol volume ratio =1 = 4) onto the catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 5mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 9
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (3) soaking for 48h at 160 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with the thickness of 40 μm.
Step S2, preparing a catalyst coating film: 1) Firstly, mixing a carbon-supported platinum electrocatalyst with platinum content of 50%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol in a mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using ultrasonic spraying equipment to form a catalyst layer 21 so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, a methanol solution of phosphoric acid (concentrated phosphoric acid: methanol volume ratio =1 = 4) is sprayed onto the gas diffusion layer on the side to be bonded to the catalyst coating film 2 using a spray gun, and the spraying amount of phosphoric acid is controlled to be 5mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Example 10
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell in this embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the area is 3X 3cm 2 PBI membrane is soaked in molten KH 5 (PO 4 ) 2 And (3) soaking for 48h at the temperature of 140 ℃, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 5mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Comparative example 1:
the preparation of the membrane electrode of the comparative example specifically comprises the following steps;
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 And (5) soaking for 48 hours at 160 ℃ to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, filmPreparing an electrode: a gas diffusion electrode (HT 140E) of the company Advent was used, which had a structure in which a catalytic layer was attached to a gas diffusion layer, and the catalytic layer was composed of a catalyst (Pt/C) and a binder (PTFE). An ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1: 4) was sprayed onto the catalytic layer surface of the gas diffusion electrode using a spray gun, and the spraying amount of phosphoric acid was controlled to be 5mg/cm by controlling the spraying time 2 (ii) a Preparing a fuel cell membrane electrode by adopting a CCS method, aligning and jointing catalyst layers of two gas diffusion electrodes and a PBI-doped molten proton conductor electrolyte membrane, and assembling the membrane electrode.
Comparative example 2:
the preparation of the membrane electrode of the comparative example specifically comprises the following steps;
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the area is 3X 3cm 2 PBI membrane is soaked in molten KH 5 (PO 4 ) 2 And soaking for 48 hours at 140 ℃ to obtain the PBI-doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a membrane electrode: an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) was sprayed onto the surface of the catalyst layer of the gas diffusion electrode using a spray gun using a gas diffusion electrode (HT 140E) of Advent corporation, and the spraying amount of phosphoric acid was controlled to 5mg/cm by controlling the spraying time 2 (ii) a Preparing a fuel cell membrane electrode by adopting a CCS method, aligning and jointing catalyst layers of two gas diffusion electrodes and a PBI-doped molten proton conductor electrolyte membrane, and assembling the membrane electrode.
Comparative example 3
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 The PBI membrane is soaked in the molten CsH 5 (PO 4 ) 2 Soaking for 48h at 160 deg.C to obtain polybenzimidazoleAzole (PBI) doped molten proton conductor electrolyte membrane with a thickness of 40 μm.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 50%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using ultrasonic spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, the gas diffusion layer and the catalyst layer are not treated by phosphoric acid;
step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Comparative example 4
The structure of a fuel cell membrane electrode according to this embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 PBI membrane is soaked in molten KH 5 (PO 4 ) 2 Soaking for 48h at 140 deg.C to obtain Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with thickness of 40 μm.
Step S2, preparing a catalyst coating film: 1) Firstly, mixing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, the gas diffusion layer and the catalyst layer are not treated by phosphoric acid;
step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Comparative example 5
The structure of a fuel cell membrane electrode according to this embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness was 35 μm and the area was 3X 3cm 2 PBI membrane is soaked in molten CsH 5 (PO 4 ) 2 Soaking for 48h at 160 ℃ to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Comparative example 6
The structure of the membrane electrode of the fuel cell related to the embodiment is shown in fig. 2.
As shown in fig. 1, the method for preparing a membrane electrode of a fuel cell of the present embodiment specifically includes the following steps:
step S1, preparing a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane 22: the thickness is 35 μm, the areaIs 3X 3cm 2 PBI membrane is soaked in molten CsH 5 (PO 4 ) 2 And soaking for 48 hours at 160 ℃ to obtain the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with the thickness of 40 mu m.
Step S2, preparing a catalyst coating film: 1) Firstly, preparing a carbon-supported platinum electrocatalyst with the platinum content of 20%, a PTFE (polytetrafluoroethylene) binder, deionized water and isopropanol according to the mass ratio of 1:0.4:5:5, mixing and ultrasonically stirring to obtain catalyst slurry; 2) Coating the catalyst slurry prepared in the step 1) on two sides of the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane obtained in the step S1 by using spray gun spraying equipment to form a catalyst layer 21, so as to prepare a catalyst coating membrane 2, and drying for later use;
step S3, spraying an ethanol solution of phosphoric acid (concentrated phosphoric acid: ethanol volume ratio =1 = 4) onto catalytic layer 21 using a spray gun, and controlling the spraying amount of phosphoric acid to be 30mg/cm by controlling the spraying time 2 ；
Step S4, preparing a membrane electrode: the membrane electrode assembly is assembled by placing the gas diffusion layers 1 on both sides of the catalyst coated membrane 2.
Performance testing of examples and comparative examples
The membrane electrodes obtained in the examples and the comparative examples are assembled into a single cell for testing, hydrogen and oxygen are respectively introduced into the anode and the cathode of the single cell, the gas flow rates of the hydrogen and the oxygen are both 0.4L/min, and the output performance of the fuel cell is tested. And, the PBI-based doped molten proton conductor (CsH) 5 (PO 4 ) 2 ) The operation temperature of the fuel cell assembled by the membrane electrode of the electrolyte membrane is 180 ℃; PBI (Poly-p-phenylene-bis-phenyleneisophthalamide) -based doped fused proton conductor (KH) 5 (PO 4 ) 2 ) The fuel cell, in which the membrane electrode of the electrolyte membrane was assembled, was operated at 150 ℃.
The numbers and main features of the membrane electrodes of the fuel cells prepared in each of the examples and comparative examples, and the output performance of the fuel cell using the membrane electrode assemblies prepared are shown in table 1.
TABLE 1
Comparative example 1 and comparative example 1 (both PBI doped CsH) 5 (PO 4 ) 2 Electrolyte membrane), and example 10 and comparative example 2 (both using PBI doped KH) 5 (PO 4 ) 2 Electrolyte membrane), it was found that, also with phosphoric acid coated on the catalytic layer, the peak power density of the fuel cell was significantly higher for the CCM type membrane electrode than for the CCS type membrane electrode. This is because, for a CCM-type membrane electrode, the catalytic layer adheres to the electrolyte membrane, the interface contact between the catalyst and the electrolyte membrane is better, and accordingly the interface resistance is smaller, resulting in higher output power density; for CCS type membrane electrodes, a gas diffusion electrode (a catalyst layer is attached to a gas diffusion layer) is attached to an electrolyte membrane, and the membrane electrode is assembled, so that the interface between the catalyst layer on the gas diffusion electrode and the electrolyte membrane has poor contact, and accordingly, the interface resistance is higher, resulting in lower output power density.
Comparative example 1 and comparative example 3 (both PBI doped CsH) 5 (PO 4 ) 2 Electrolyte membrane), and example 10 and comparative example 4 (both using PBI doped KH) 5 (PO 4 ) 2 Electrolyte membrane), it has been found that, for CCM-type membrane electrodes, the application of phosphoric acid on the catalytic layer has a critical effect on fuel cell performance. This is because the catalytic layer is made of Pt/C and a binder (PTFE or the like) and does not have a proton conductor. The phosphoric acid is coated on the catalytic layer, and permeates into the catalytic layer formed by Pt/C and a binder (PTFE and the like), so that a proton transmission channel can be established in the catalytic layer, the proton transmission resistance in the catalytic layer is obviously reduced, and the output performance of the fuel cell of the membrane electrode is obviously improved.
The amount of phosphoric acid on the catalytic layer has a large effect on the fuel cell performance. The CCM-type membrane electrodes of examples 1 to 6 had higher peak power densities of fuel cells as compared with comparative examples 5 and 6, and it was found that phosphoric acid (1 to 20 mg/cm) was sprayed on the catalytic layer 2 )，Phosphoric acid permeates into the catalyst layer formed by Pt/C and a binder (PTFE and the like), so that a proton transmission channel in the catalyst layer can be effectively improved, the proton transmission resistance in the catalyst layer is reduced, and the electric output performance of the membrane electrode is improved. However, too little phosphoric acid makes it difficult to establish a sufficient proton conduction channel, while too much phosphoric acid causes it to block a gas transmission channel.
Unlike examples 1-6, in which phosphoric acid is coated on the catalytic layer by spray coating, examples 7 and 8, in which phosphoric acid is coated on the catalytic layer by blade coating and slit coating, respectively, the membrane electrode assembled by the two methods can also obtain good peak power density of the fuel cell.
Comparing example 1, example 7 and example 8, it can be seen that compared with PBI and PVDF as binders, the strong hydrophobic surface property of PTFE used in example 1 enables the PTFE to establish gas transmission channels in the catalyst layer, and prevents phosphoric acid from excessively blocking the gas channels, thereby obtaining good output performance of the fuel cell, and therefore PTFE can be used as the first choice of the binder in the membrane electrode catalyst layer.
Example 9 phosphoric acid was sprayed on the gas diffusion layer, and after the membrane electrode was assembled in CCM, the phosphoric acid on the gas diffusion layer could wet the catalytic layer on the electrolyte, allowing the catalytic layer to establish proton conducting channels, and also achieving better performance.
In summary, the invention provides a membrane electrode based on a Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and a preparation method thereof, wherein the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane with good mechanical strength, dimensional stability and proton conductivity is coated with a catalyst slurry, and the membrane electrode is prepared by a CCM method, so that good interface combination between the Polybenzimidazole (PBI) doped molten proton conductor electrolyte membrane and a catalyst layer can be realized, and the material transmission resistance of the membrane electrode interface is reduced; the catalyst layer and/or the gas diffusion layer are/is coated with trace phosphoric acid, so that a proton transmission channel in the membrane electrode is improved, and the proton transmission resistance in the catalyst layer is reduced, so that the prepared membrane electrode has excellent electric output performance.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (7)
1. A fuel cell membrane electrode comprising a catalyst coated membrane (2) and a gas diffusion layer (1), the gas diffusion layer (1) being placed on both sides of the catalyst coated membrane (2), the catalyst coated membrane (2) comprising a polybenzimidazole-doped molten proton conductor electrolyte membrane (22) and a catalytic layer (21), the catalytic layer (21) being coated on one side or both sides of the polybenzimidazole-doped molten proton conductor electrolyte membrane (22); one surface of the gas diffusion layer (1) which is attached to the catalyst coating film (2) and/or the catalyst layer (21) is coated with phosphoric acid, and the content of the phosphoric acid is 1-20mg/cm 2 (ii) a The preparation method of the polybenzimidazole doped molten proton conductor electrolyte membrane (22) comprises the following steps:
1) Putting the solid proton conductor in a high-temperature oven to convert the solid proton conductor into a molten proton conductor;
2) And soaking the polybenzimidazole membrane in a molten proton conductor, taking out the polybenzimidazole membrane after the soaking time is finished, and removing the proton conductor on the surface of the membrane to obtain the polybenzimidazole doped molten proton conductor electrolyte membrane (22).
2. A method of making a fuel cell membrane electrode assembly according to claim 1, comprising the steps of:
s1, preparing a polybenzimidazole doped molten proton conductor electrolyte membrane (22);
step S2, coating catalyst slurry on one side or two sides of the polybenzimidazole-doped molten proton conductor electrolyte membrane (22) prepared in step S1 to form a catalyst layer (21) so as to prepare a catalyst coating membrane (2);
step S3, one surface of the gas diffusion layer (1) which is attached to the catalyst coating film (2) and/or the catalystApplying phosphoric acid on the layer (21); the phosphoric acid coating mode is spraying, and the phosphoric acid coating content is 1-20mg/cm 2 ；
And S4, placing the gas diffusion layers (1) on two sides of the catalyst coating membrane (2) to assemble the fuel cell membrane electrode.
3. The method for preparing a fuel cell membrane electrode assembly according to claim 2, wherein said solid proton conductor is CsH 5 (PO 4 ) 2 Or KH 5 (PO 4 ) 2 。
4. The method for preparing a fuel cell membrane electrode according to claim 2, wherein the soaking time of the polybenzimidazole membrane in a proton conductor in a molten state is 6 to 72 hours.
5. The method for preparing a fuel cell membrane electrode according to claim 2, wherein in step S2, the catalyst slurry comprises a mixture of a binder, a catalyst and a solvent, wherein the binder is one or more of PBI, PTFE, PVDF and PVF, the solvent is one or more of ethanol, methanol, isopropanol, n-propanol and n-butanol, and the catalyst is a carbon-supported platinum electrocatalyst, wherein the mass ratio of platinum to carbon support is (1-9): (9-1).
6. The method for preparing a fuel cell membrane electrode according to claim 2, wherein in step S2, the catalyst slurry is applied by spray coating, blade coating, or slit extrusion coating.
7. The method for preparing a fuel cell membrane electrode assembly according to claim 2, wherein a mixed solution of concentrated phosphoric acid and an alcohol selected from one or more of methanol, ethanol, n-propanol, and isopropanol is used for coating phosphoric acid.
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| CN107331883A (en) * | 2017-05-10 | 2017-11-07 | 上海交通大学 | A kind of middle temperature proton exchange film and preparation method thereof |
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