CN113937303A - Catalytic layer electrode composition, catalytic layer electrode comprising same and membrane electrode - Google Patents
Catalytic layer electrode composition, catalytic layer electrode comprising same and membrane electrode Download PDFInfo
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- CN113937303A CN113937303A CN202111199477.3A CN202111199477A CN113937303A CN 113937303 A CN113937303 A CN 113937303A CN 202111199477 A CN202111199477 A CN 202111199477A CN 113937303 A CN113937303 A CN 113937303A
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group 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]
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
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Abstract
The invention provides a catalytic layer electrode composition, a catalytic layer electrode comprising the same and a membrane electrode, wherein the catalytic layer electrode composition comprises a combination of a catalyst, a perfluorosulfonic acid polymer and supported perfluorosulfonic acid polymer particles; the supported perfluorosulfonic acid polymer particles comprise carrier particles containing hydrophilic groups and perfluorosulfonic acid polymers supported on the carrier particles. The catalytic layer electrode composition has the advantages that the pore structure of the catalytic layer formed by the catalytic layer electrode composition is uniformly distributed, the porosity is high, the PFSA is uniformly distributed in the catalytic layer, the using amount of the PFSA is reduced, the wrapping phenomenon of the PFSA on the catalyst is reduced, the contact of reaction gas and components of the catalyst is promoted, a three-phase interface is increased, the utilization rate of the catalyst is improved, the gas diffusion and mass transfer processes in the reaction are enhanced, the proton transfer in the catalytic layer is promoted, the dynamic electrochemical reaction rate is improved, and the comprehensive performance of the catalytic layer electrode, the membrane electrode and the fuel cell containing the catalytic layer electrode composition is obviously improved.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a catalytic layer electrode composition, a catalytic layer electrode comprising the catalytic layer electrode composition and a membrane electrode comprising the catalytic layer electrode composition.
Background
A fuel cell is an electrochemical cell whose main operating principle is to convert chemical energy in a fuel and an oxidant directly into electrical energy through an oxidation-reduction reaction. The proton exchange membrane fuel cell, as an important branch in the field of fuel cells, has the general characteristics of fuel cells, and has the outstanding advantages of high starting speed at room temperature, small volume, no electrolyte loss, easy water drainage, long service life, high specific power and specific energy and the like, thereby being one of the most promising new energy power products.
The core component of a proton exchange membrane fuel cell is a membrane electrode, which is a place for the fuel cell to perform oxidation-reduction reaction and mainly comprises a Gas Diffusion Layer (GDL), a Catalyst Layer (CL), a Proton Exchange Membrane (PEM) and the like. Currently, the Membrane electrode is usually prepared by coating a Catalyst layer directly on a proton Membrane to form a Catalyst Coated Membrane (CCM), and then bonding the CCM and a GDL together to prepare a Membrane electrode, while another common Membrane electrode preparation process is to coat a Catalyst slurry directly on the GDL to prepare a Gas Diffusion Electrode (GDE) and then bond the GDE with the proton exchange Membrane. At present, the preparation method of the membrane electrode only focuses on two processes of CCM and GDE, and the two processes are both formed by coating and drying catalyst slurry to form a catalyst layer and tightly combining the catalyst layer with a proton exchange membrane, so that the catalyst layer structure generally comprises catalyst particles and ionic polymers, the catalyst particles are mutually stacked, the porosity of the catalyst layer is low, the gas diffusion and mass transfer processes are not facilitated, the utilization rate of the catalyst is not high, and the performance of a fuel cell is seriously influenced. Therefore, the optimization of the catalytic layer structure in the membrane electrode has great significance for improving the performance of the fuel cell.
For example, CN112259768A discloses a fuel cell membrane electrode with gradient-distributed catalyst layers and a preparation method thereof, wherein a first catalyst layer raw material of the fuel cell membrane electrode consists of a particulate catalyst, water, a perfluorosulfonic acid polymer solution and isopropanol, and a second catalyst layer raw material consists of a large-particle composite catalyst, water, a perfluorosulfonic acid polymer solution and isopropanol, and the preparation method comprises: uniformly spraying the first catalyst slurry on the surface of a proton exchange membrane through ultrasonic atomization, drying and shaping, spraying the second catalyst slurry on a first catalyst layer through ultrasonic atomization, drying and shaping, and hot pressing and attaching carbon fiber paper; the preparation method can improve the catalytic efficiency of the membrane electrode of the fuel cell, but does not fundamentally solve the problems that catalyst particles are wrapped by polymers and are tightly stacked, and the catalyst efficiency is poor. CN109713321A discloses a membrane electrode with adjustable pore structure and its preparation method, the membrane electrode comprises: the anode catalyst layer and the porous cathode catalyst layer are arranged on the proton exchange membrane; the anode catalyst layer is made of anode catalyst slurry, and the cathode catalyst layer is made of cathode catalyst slurry. The cathode catalyst layer and the anode catalyst layer respectively comprise a solid phase component consisting of a catalyst and ionic resin and a pore structure with an irregular shape; the pore structure includes: primary pores formed by the agglomeration and accumulation of the solid phase components and secondary pores left after the pore-forming agent is removed; the membrane electrode uses nano-oxide to form pores in the cathode catalyst layer, so that the porosity of the cathode catalyst layer is increased, and the pore size distribution in the catalyst layer is changed, but the pore size distribution of the catalyst layer cannot be controlled in the pore-forming agent removing process, so that irregular macropores are generated in the catalyst layer, the membrane electrode is not beneficial to long-term application in the later stage of a fuel cell, the interface contact resistance is increased, and the service life of the membrane electrode is shortened.
Therefore, the existing membrane electrode still can not effectively improve the utilization rate of the catalyst, and in the electrochemical reaction process, the transfer path of reaction gas and proton is tortuous, which is not beneficial to the gas diffusion, the mass transfer process and the proton conduction, thereby seriously influencing the performance of the fuel cell.
Therefore, there is a need in the art to develop a membrane electrode that can improve catalyst utilization, enhance gas diffusion and mass transfer processes, and meet the application requirements of fuel cells.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a catalytic layer electrode composition, a catalytic layer electrode comprising the catalytic layer electrode composition and a membrane electrode comprising the catalytic layer electrode composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a catalytic layer electrode composition comprising a combination of a catalyst, a perfluorosulfonic acid Polymer (PFSA), and supported perfluorosulfonic acid polymer particles; the supported perfluorosulfonic acid polymer particles include support particles containing a hydrophilic group, and a perfluorosulfonic acid Polymer (PFSA) supported on the support particles.
The catalytic layer electrode composition provided by the invention comprises supported perfluorosulfonic acid polymer particles, wherein PFSA interacts with hydrophilic groups on carrier particles in the supported perfluorosulfonic acid polymer particles, so that the supported perfluorosulfonic acid polymer particles are stably fixed on the carrier particles, on one hand, the dosage of PFSA resin in the catalytic layer electrode composition can be reduced, and the phenomenon that a catalyst is wrapped by PFSA polymer is reduced, on the other hand, the introduction of the supported perfluorosulfonic acid polymer particles can improve the porosity of a catalyst layer, reduce the diffusion resistance and mass transfer resistance of reaction gas, and increase the number of three-phase interfaces in a membrane electrode, so that the utilization rate of the catalyst is remarkably improved; moreover, hydrophilic groups on the carrier particles can combine with water molecules in the membrane electrode catalyst layer to play a role in transferring protons, so that the proton transfer resistance of the catalyst layer is further reduced, and the performance is improved. The catalyst layer electrode composition is applied to a catalyst layer electrode and a membrane electrode, the pore structure in the formed catalyst layer is uniformly distributed, the porosity is high, PFSA polymers are promoted to be uniformly distributed in the catalyst layer, the using amount of PFSA is reduced, the wrapping phenomenon of PFSA on the catalyst is reduced, so that the contact of reaction gas and components of the catalyst is promoted, a three-phase interface is increased, the utilization rate of the catalyst is improved, and the gas diffusion and mass transfer processes in the reaction are enhanced; meanwhile, the surface of the carrier particle contains a conductive hydrophilic group, so that proton transfer in the catalyst layer can be promoted, the kinetic electrochemical reaction rate is improved, and the performance of the fuel cell can be further improved.
Preferably, the hydrophilic group includes any one of a hydroxyl group, a carboxyl group, an amino group, a phosphoric acid group, or an ether bond or a combination of at least two thereof. The hydrophilic groups on the carrier particles can form hydrogen bonds with functional groups in the PFSA, or form chemical bonds (such as ester bonds and the like) through chemical reaction, so that the PFSA is firmly loaded on the carrier particles; meanwhile, the hydrophilic groups can combine with water in the catalyst layer to realize proton transfer, so that the proton transfer resistance of the catalyst layer is further reduced, and the gas diffusion and mass transfer processes are enhanced.
Preferably, the catalyst is a platinum-based catalyst, more preferably a platinum-carbon (Pt/C) catalyst.
Preferably, the platinum content of the platinum-carbon catalyst is 20-70% by mass, for example, 21%, 23%, 25%, 27%, 29%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65% or 68%, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention does not provide an exhaustive list of specific values included in the range.
The mass ratio of the perfluorosulfonic acid polymer to the carbon support in the platinum-carbon catalyst is preferably 1 (1 to 10), and may be, for example, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.2, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1: 9.5.
Preferably, the particle size of the carrier particles is 0.01-1 μm, such as 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 0.95 μm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the support particles are selected from any one of inorganic particles, organic particles or organic-inorganic hybrid particles or a combination of at least two thereof.
Preferably, the inorganic particles comprise any one of silica, zirconia, titania, zinc oxide, ceria, manganese dioxide, boehmite, mica, or montmorillonite, or a combination of at least two thereof.
The mass ratio of the carrier particles to the perfluorosulfonic acid polymer in the supported perfluorosulfonic acid polymer particles is preferably 1 (5 to 10), and may be, for example, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1: 9.5.
Preferably, the supported perfluorosulfonic acid polymer particles are prepared by a process comprising: mixing the carrier particles with a perfluorosulfonic acid polymer solution to obtain a dispersion liquid; and reacting the dispersion liquid to obtain the loaded perfluorosulfonic acid polymer particles.
The mass ratio of the carrier particles to the perfluorosulfonic acid polymer in the dispersion is preferably 1 (5-10), and may be, for example, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, or 1: 9.5.
Preferably, the dispersion liquid further comprises an alcohol solvent.
Preferably, the alcoholic solvent includes any one of methanol, ethanol, isopropanol, n-propanol, n-butanol or tert-butanol or a combination of at least two thereof.
Preferably, the reaction temperature is 70-120 ℃, for example, it may be 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃ or 115 ℃, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the temperature of the reaction is such that the dispersion is able to achieve reflux.
Preferably, the reaction time is 12-48 h, for example, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h or 44h, and the specific values therebetween are not exhaustive, and for brevity, the invention is not exhaustive.
Preferably, the reaction further comprises a drying step.
Preferably, the mass ratio of the catalyst to the perfluorosulfonic acid polymer is (1 to 10):1, and may be, for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, or 9.5: 1.
Preferably, the mass ratio of the catalyst to the supported perfluorosulfonic acid polymer particles is (5-15: 1), and may be, for example, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1 or 14.5: 1.
The mass ratio referred to in the present invention is a mass ratio calculated as a solid content (effective component), and does not include a solvent and an auxiliary (e.g., a dispersant, an emulsifier, etc.) therein.
In a second aspect, the present invention provides a catalyst ink comprising a catalytic layer electrode composition according to the first aspect in combination with a solvent.
Preferably, the solid content of the catalyst slurry is 10-20%, for example, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, or 19.5%, and specific values therebetween are not exhaustive and are not intended to limit the scope of the invention to the specific values included in the ranges for brevity and conciseness.
Preferably, the solvent comprises water and/or an alcohol solvent.
Preferably, the alcoholic solvent includes any one of methanol, ethanol, isopropanol, n-propanol, n-butanol or tert-butanol or a combination of at least two thereof.
Illustratively, the preparation method of the catalyst paste includes: and mixing the catalyst layer electrode composition with a solvent, and uniformly dispersing to obtain the catalyst slurry.
In a third aspect, the invention provides a catalytic layer electrode, which comprises a first catalytic layer, a proton exchange membrane and a second catalytic layer which are sequentially arranged; the material of the first catalytic layer and/or the second catalytic layer comprises a catalytic layer electrode composition as described in the first aspect.
Preferably, the materials of the first and second catalytic layers are both catalytic layer electrode compositions as described in the first aspect.
Illustratively, the preparation method of the catalytic layer electrode comprises the following steps: mixing the catalytic layer electrode composition with a solvent to obtain catalyst slurry; and coating the catalyst slurry on a transfer printing base membrane, drying, and then transferring the catalyst slurry to the surface of a proton exchange membrane to obtain the catalyst layer electrode.
Illustratively, the preparation method of the catalytic layer electrode comprises the following steps: mixing the catalytic layer electrode composition with a solvent to obtain catalyst slurry; and coating the catalyst slurry on the surface of a proton exchange membrane, and drying to obtain the catalyst layer electrode.
In a fourth aspect, the present invention provides a membrane electrode comprising a catalysed layer electrode according to the third aspect.
Preferably, the membrane electrode comprises a laminated electrode and a frame membrane outside the laminated electrode, and the laminated electrode comprises a first gas diffusion layer, the catalytic layer electrode and a second gas diffusion layer which are arranged in sequence.
In a fifth aspect, the present invention provides a fuel cell comprising a membrane electrode according to the fourth aspect.
Compared with the prior art, the invention has the following beneficial effects:
in the catalytic layer electrode composition provided by the invention, the supported perfluorosulfonic acid polymer particles are used and matched with the catalyst and the perfluorosulfonic acid polymer, so that the pore structure of a catalyst layer formed by the catalytic layer electrode composition is uniformly distributed, the porosity is high, and PFSA is uniformly distributed in the catalytic layer, the consumption of PFSA is reduced, the wrapping phenomenon of PFSA on the catalyst is reduced, the contact of reaction gas and components of the catalyst is promoted, a three-phase interface is increased, the utilization rate of the catalyst is improved, and the gas diffusion and mass transfer processes in the reaction are enhanced. Meanwhile, the carrier particles in the loaded perfluorosulfonic acid polymer particles contain hydrophilic groups, so that proton transfer in the catalyst layer can be promoted, the dynamic electrochemical reaction rate is improved, and the comprehensive performance of the catalyst layer electrode, the membrane electrode and the fuel cell containing the same is remarkably improved.
Drawings
FIG. 1 is a flow chart of a process for preparing a membrane electrode provided in example 1;
FIG. 2 is a flow chart of a process for preparing a membrane electrode provided in example 6;
FIG. 3 is a test chart of polarization curves of the membrane electrodes provided in examples 1 to 4 and comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following examples and comparative examples of the present invention, the platinum-carbon catalyst, the perfluorosulfonic acid polymer solution, the carrier particles and the solvent are commercially available products and commercially available. The proton exchange membrane, the gas diffusion layer and the frame membrane used for preparing the membrane electrode are all materials known in the art and can be purchased and obtained through market approaches, and are not described in detail for the sake of simplicity.
Example 1
This example provides a catalytic layer electrode composition comprising 1.2g of platinum carbon catalyst (Pt/C catalyst, Pt mass% 47%), 1g of perfluorosulfonic acid polymer solution (PFSA solution, concentration 20%) and 0.12g of supported perfluorosulfonic acid Polymer (PFSA) particles;
wherein the supported perfluorosulfonic acid polymer particles comprise carrier particles (silica particles, the particle diameter is 0.05 mu m, and the surface of the carrier particles is provided with hydroxyl) containing hydroxyl and PFSA supported on the carrier particles, and the preparation method comprises the following steps: mixing 0.5g of carrier particles, 30mL of ethanol and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6 hours to form a uniform and stable dispersion liquid; and stirring the dispersion liquid for reflux reaction for 48 hours to react hydroxyl on the surface of the carrier particle with PFSA to obtain the PFSA-loaded particle.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) mixing 1.2g of Pt/C catalyst, 1g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol according to the formula amount, and uniformly dispersing by stirring at a high speed for 2 hours to obtain catalyst slurry with the solid content of about 17.4%;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a Proton Exchange Membrane (PEM) through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer (the thickness is 210 mu m) and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2(ii) a The preparation process flow chart of the membrane electrode is shown in figure 1.
Example 2
This example provides a catalytic layer electrode composition comprising 1.2g of Pt/C catalyst (47% Pt by mass), 1.2g of PFSA solution (20% concentration) and 0.12g of supported PFSA particles;
wherein, the PFSA-loaded particle comprises a carrier particle (mica particle with the particle diameter of 0.1 μm and hydroxyl group on the surface) containing hydroxyl group and PFSA loaded on the carrier particle, and the preparation method comprises the following steps: mixing 0.5g of carrier particles, 30mL of ethanol and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6 hours to form a uniform and stable dispersion liquid; and stirring the dispersion liquid for reflux reaction for 48 hours to react hydroxyl on the surface of the carrier particle with PFSA to obtain the PFSA-loaded particle.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) according to the formula amount, 1.2g of Pt/C catalyst, 1.2g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol are mixed and uniformly dispersed by high-speed stirring for 2 hours to obtain catalyst slurry with the solid content of 17.5 percent;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a proton exchange membrane through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2。
Example 3
This example provides a catalytic layer electrode composition comprising 1.2g of Pt/C catalyst (47% Pt by mass), 1.2g of PFSA solution (20% concentration) and 0.12g of supported PFSA particles;
wherein, the PFSA-loaded particles comprise carrier particles (boehmite particles with the particle size of 0.8 μm and hydroxyl groups on the surface) containing hydroxyl groups and PFSA loaded on the carrier particles, and the preparation method comprises the following steps: mixing 0.5g of carrier particles, 30mL of isopropanol and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6h to form a uniform and stable dispersion; and stirring the dispersion liquid for reflux reaction for 48 hours to react hydroxyl on the surface of the carrier particle with PFSA to obtain the PFSA-loaded particle.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) according to the formula amount, 1.2g of Pt/C catalyst, 1.2g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol are mixed and uniformly dispersed by high-speed stirring for 2 hours to obtain catalyst slurry with the solid content of 17.5 percent;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a proton exchange membrane through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2。
Example 4
This example provides a catalytic layer electrode composition comprising 1.2g of Pt/C catalyst (47% Pt by mass), 1.2g of PFSA solution (20% concentration) and 0.12g of supported PFSA particles;
wherein, the PFSA-loaded particles comprise carrier particles (montmorillonite particles with the particle diameter of 0.2 μm and hydroxyl groups on the surface) containing hydroxyl groups and PFSA loaded on the carrier particles, and the preparation method comprises the following steps: mixing 0.5g of carrier particles, 30mL of ethanol and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6 hours to form a uniform and stable dispersion liquid; and stirring the dispersion liquid for reflux reaction for 48 hours to react hydroxyl on the surface of the carrier particle with PFSA to obtain the PFSA-loaded particle.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) according to the formula amount, 1.2g of Pt/C catalyst, 1.2g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol are mixed and uniformly dispersed by high-speed stirring for 2 hours to obtain catalyst slurry with the solid content of 17.5 percent;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a proton exchange membrane through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2。
Example 5
This example provides a catalytic layer electrode composition comprising 1.2g of Pt/C catalyst (47% Pt by mass), 1.2g of PFSA solution (20% concentration) and 0.12g of supported PFSA particles;
wherein, the PFSA-loaded particles comprise carrier particles (manganese dioxide particles with the particle diameter of 0.1 μm and hydroxyl groups on the surface) containing hydroxyl groups and PFSA loaded on the carrier particles, and the preparation method comprises the following steps: mixing 0.5g of carrier particles and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6h to form a uniform and stable dispersion; and stirring and refluxing the dispersion liquid in an environment of 100 ℃ for reaction for 48 hours to react hydroxyl on the surfaces of the carrier particles with PFSA to obtain the PFSA-loaded particles.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) according to the formula amount, 1.2g of Pt/C catalyst, 1.2g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol are mixed and uniformly dispersed by high-speed stirring for 2 hours to obtain catalyst slurry with the solid content of 17.5 percent;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a proton exchange membrane through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2。
Example 6
This example provides a catalytic layer electrode composition comprising 1.2g of Pt/C catalyst (47% Pt by mass), 1g of PFSA solution (20% concentration) and 0.12g of supported PFSA particles;
wherein, the PFSA-loaded particles comprise carrier particles (cerium oxide particles with the particle diameter of 0.05 μm and hydroxyl groups on the surface) containing hydroxyl groups and PFSA loaded on the carrier particles, and the preparation method comprises the following steps: mixing 0.5g of carrier particles and 20g of PFSA solution (with the concentration of 20%), and stirring at high speed for 6h to form a uniform and stable dispersion; and stirring and refluxing the dispersion liquid in an environment of 80 ℃ for reaction for 48 hours to react hydroxyl on the surfaces of the carrier particles with PFSA to obtain the PFSA-loaded particles.
The embodiment also provides catalyst slurry, a catalytic layer electrode and a membrane electrode which comprise the catalytic layer electrode composition, and the specific preparation method comprises the following steps:
(1) according to the formula amount, 1.2g of Pt/C catalyst, 1g of PFSA solution, 0.12g of load PFSA particles, 4g of deionized water and 2.4g of isopropanol are mixed and uniformly dispersed by high-speed stirring for 2 hours to obtain catalyst slurry with the solid content of 17.5 percent;
(2) coating the catalyst slurry obtained in the step (1) on two surfaces of a Proton Exchange Membrane (PEM), and drying to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-in-one membrane electrode; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2(ii) a The flow chart of the preparation process of the membrane electrode is shown in figure 2.
Comparative example 1
This comparative example provides a catalytic layer electrode composition comprising 1.2g of a Pt/C catalyst (47% Pt by mass) and 2g of a PFSA solution (20% concentration).
The comparative example also provides catalyst slurry, a catalytic layer electrode and a membrane electrode comprising the catalytic layer electrode composition, and the specific preparation method is as follows:
(1) mixing 1.2g of Pt/C catalyst, 2g of PFSA solution, 4g of deionized water and 2.4g of isopropanol according to the formula amount, and uniformly dispersing by stirring at a high speed for 2 hours to obtain catalyst slurry with the solid content of 16.7%;
(2) coating the catalyst slurry obtained in the step (1) on a transfer printing base film through a scraper, and after drying, transferring the catalyst slurry onto two surfaces of a proton exchange membrane through a transfer printing method to obtain a catalyst layer electrode;
(3) hot-pressing and attaching the catalytic layer electrode obtained in the step (2) with a gas diffusion layer and a frame membrane to obtain a seven-layer structureA membrane electrode of one; the Pt loading capacity of the cathode side in the membrane electrode is 0.4mg/cm2(ii) a The loading capacity of the anode side is 0.1mg/cm2。
And (3) performance testing:
the Membrane Electrodes (MEAs) provided in the foregoing examples and comparative examples were respectively assembled into fuel cells and tested for performance under the following conditions: the temperature is 80 ℃, the humidity is 100%, the flow rate of hydrogen and air is 1.3:2.0 according to the metering ratio, the back pressure of a hydrogen end is 0.2MPa, and the back pressure of an air end is 0.2 MPa; fig. 3 shows polarization curve test charts of the membrane electrodes provided in examples 1 to 4 and comparative example 1.
As can be seen from fig. 3: under the same current density, the voltage of the membrane electrode provided by the invention in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 is larger than that of the comparative example 1, the power density of the embodiment 1-4 is higher than that of the comparative example 1, and the maximum power density of the embodiment 1-4 is much higher than that of the comparative example 1, which shows that the performance of the fuel cell comprising the membrane electrode provided by the invention in the embodiment 1, the embodiment 2, the embodiment 3 and the embodiment 4 is better than that of the fuel cell in the comparative example 1, namely the performance of the catalyst layer electrode and the catalyst layer electrode composition is better.
Generally, the supported perfluorosulfonic acid polymer particles are matched with the catalyst and the perfluorosulfonic acid polymer, so that the formed catalyst layer has uniform pore structure distribution and high porosity, and PFSA is uniformly distributed in the catalyst layer, the dosage of PFSA is reduced, the wrapping phenomenon of PFSA on the catalyst is reduced, the contact of reaction gas and components of the catalyst is promoted, a three-phase interface is increased, the utilization rate of the catalyst is improved, and the gas diffusion and mass transfer processes in the reaction are enhanced, so that the performances of the electrode of the catalyst layer, the membrane electrode and the fuel cell containing the supported perfluorosulfonic acid polymer particles are improved.
The applicant states that the present invention is illustrated by the above examples to show a catalytic layer electrode composition, a catalytic layer electrode comprising the same, and a membrane electrode of the present invention, but the present invention is not limited to the above process steps, i.e. the present invention is not meant to be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A catalytic layer electrode composition, characterized in that the catalytic layer electrode composition comprises a combination of a catalyst, a perfluorosulfonic acid polymer, and supported perfluorosulfonic acid polymer particles;
the supported perfluorosulfonic acid polymer particles comprise carrier particles containing hydrophilic groups and perfluorosulfonic acid polymers supported on the carrier particles.
2. The catalytic layer electrode composition of claim 1, wherein the catalyst is a platinum carbon catalyst;
preferably, the mass percentage of platinum in the platinum-carbon catalyst is 20-70%;
preferably, the mass ratio of the perfluorinated sulfonic acid polymer to the carbon carrier in the platinum-carbon catalyst is 1 (1-10).
3. The catalytic layer electrode composition according to claim 1 or 2, wherein the particle size of the support particles is 0.01 to 1 μm;
preferably, the carrier particles are selected from any one of inorganic particles, organic particles or organic-inorganic hybrid particles or a combination of at least two of them;
preferably, the inorganic particles comprise any one of or a combination of at least two of silica, zirconia, titania, zinc oxide, ceria, manganese dioxide, boehmite, mica, or montmorillonite;
preferably, the mass ratio of the carrier particles to the perfluorosulfonic acid polymer in the supported perfluorosulfonic acid polymer particles is 1 (5-10).
4. The catalytic layer electrode composition according to any one of claims 1 to 3, wherein the supported perfluorosulfonic acid polymer particles are prepared by a method comprising: mixing the carrier particles with a perfluorosulfonic acid polymer solution to obtain a dispersion liquid; reacting the dispersion liquid to obtain the loaded perfluorosulfonic acid polymer particles;
preferably, the mass ratio of the carrier particles to the perfluorosulfonic acid polymer in the dispersion liquid is 1 (5-10);
preferably, the dispersion liquid also comprises an alcohol solvent;
preferably, the reaction temperature is 70-120 ℃;
preferably, the reaction time is 12-48 h;
preferably, the reaction further comprises a drying step.
5. The catalytic layer electrode composition according to any one of claims 1 to 4, wherein the mass ratio of the catalyst to the perfluorosulfonic acid polymer is (1 to 10): 1;
preferably, the mass ratio of the catalyst to the supported perfluorosulfonic acid polymer particles is (5-15): 1.
6. A catalyst paste comprising the catalytic layer electrode composition according to any one of claims 1 to 5 in combination with a solvent.
7. The catalyst ink according to claim 6, wherein the solid content of the catalyst ink is 10-20%;
preferably, the solvent comprises water and/or an alcohol solvent;
preferably, the alcoholic solvent includes any one of methanol, ethanol, isopropanol, n-propanol, n-butanol or tert-butanol or a combination of at least two thereof.
8. The catalytic layer electrode is characterized by comprising a first catalytic layer, a proton exchange membrane and a second catalytic layer which are sequentially arranged; the material of the first catalytic layer and/or the second catalytic layer comprises a catalytic layer electrode composition according to any one of claims 1 to 5;
preferably, the materials of the first catalytic layer and the second catalytic layer are both catalytic layer electrode compositions according to any one of claims 1 to 5.
9. A membrane electrode, wherein the membrane electrode comprises the catalytic layer electrode of claim 8;
preferably, the membrane electrode comprises a laminated electrode and a frame membrane outside the laminated electrode, and the laminated electrode comprises a first gas diffusion layer, the catalytic layer electrode and a second gas diffusion layer which are arranged in sequence.
10. A fuel cell, characterized in that the fuel cell comprises the membrane electrode according to claim 9.
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