CN114759235B - Water-retaining layer, membrane electrode and preparation method thereof - Google Patents
Water-retaining layer, membrane electrode and preparation method thereof Download PDFInfo
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- CN114759235B CN114759235B CN202210333761.3A CN202210333761A CN114759235B CN 114759235 B CN114759235 B CN 114759235B CN 202210333761 A CN202210333761 A CN 202210333761A CN 114759235 B CN114759235 B CN 114759235B
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Classifications
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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]
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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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Abstract
The invention particularly relates to a water-retaining layer, a membrane electrode and a preparation method thereof, and belongs to the technical field of fuel cells. The water-retaining layer is arranged between the proton exchange membrane and the anode catalytic layer, and the raw materials of the water-retaining layer comprise: super absorbent resin and Nafion solution; the effective water-retaining component is super absorbent resin, and the super absorbent resin has more excellent hydrophilicity and water-retaining capacity compared with inorganic oxide and other high molecular polymers, can effectively strengthen the back diffusion of cathode generated water, can reduce the thickness of a water-retaining layer, and plays a good wetting effect on a proton exchange membrane and an anode catalytic layer while ensuring the proton conductivity, thereby realizing the high performance of a membrane electrode under the low-humidity operation condition.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a water-retaining layer, a membrane electrode and a preparation method thereof.
Background
The Membrane Electrode (MEA) is the most important component of the proton exchange membrane fuel cell, and mainly consists of a proton exchange membrane (such as Nafion membrane), an anode/cathode Catalytic Layer (CL) and an anode/cathode Gas Diffusion Layer (GDL), and its characteristics directly affect the performance of the PEMFC.
The perfluorosulfonic acid resin used as a binder in the perfluorosulfonic acid polymer membrane and the catalyst layer used in the membrane electrode of the fuel cell needs to conduct protons well in a hydrated state, and when the water content in the membrane electrode is too low, the proton conducting ability of the perfluorosulfonic acid resin in the perfluorosulfonic acid membrane and the catalyst layer is weakened or even lost.
In order to ensure proper operation of the membrane electrode, one has to provide a humidification system in the fuel cell system to humidify the gas to ensure proton conductivity of the perfluorosulfonic acid membrane and resin, the provision of the humidification system increasing the complexity, cost and energy consumption of the fuel cell system. Therefore, development of a self-humidifying membrane electrode capable of operating normally under low humidity conditions has been a hot research topic in the field of fuel cells in recent years. The self-humidification of the membrane electrode is realized, so that the power density of the system can be effectively improved, the cost and the energy consumption of the system can be reduced, the problem of water management of the proton exchange membrane fuel cell can be effectively solved, and the problems of local flooding or dry solidification in the cell can be avoided. This is of great significance for the development and large-scale commercial application of proton exchange membrane fuel cells.
Disclosure of Invention
The purpose of the application is to provide a water-retaining layer, a membrane electrode and a preparation method thereof, so as to solve the problem that the low humidity performance of the membrane electrode is not high at present.
The embodiment of the invention provides a water-retaining layer, which comprises the following raw materials: super absorbent resins and Nafion solution.
Optionally, the super absorbent resin comprises at least one of polyacrylate, starch acrylate polymer, starch-acrylonitrile graft copolymer, polyacrylic acid-acrylamide, and acrylamide-acrylonitrile-acrylic acid.
Optionally, the mass ratio of the super absorbent resin to the Nafion ionomer in the Nafion solution is 5% -30% to 70% -95%.
Optionally, the raw material of the water-retaining layer further comprises a solvent, and the solvent is a mixture of water and isopropanol.
Optionally, the mass ratio of the water to the isopropanol is 1-3:1-5.
Optionally, the mass of the Nafion ionomer in the super absorbent resin and the Nafion solution accounts for 1-10% of the mass of the raw materials.
Optionally, the mass concentration of the Nafion solution is 5% -20%.
Optionally, the thickness of the water-retaining layer is 0.5 μm-2 μm.
Based on the same inventive concept, the embodiment of the invention also provides a membrane electrode, which comprises the water-retaining layer.
Optionally, the membrane electrode further comprises a proton exchange membrane and an anode catalytic layer, and the water-retaining layer is arranged between the proton exchange membrane and the anode catalytic layer.
Optionally, the membrane electrode further comprises a proton exchange membrane, the water-retaining layer is laid on the proton exchange membrane, and the proton exchange membrane is a commercial proton exchange membrane.
Optionally, the thickness of the proton exchange membrane is 5 μm to 20 μm.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the membrane electrode, which comprises the following steps:
mixing high water absorption resin and Nafion solution in a solvent to obtain dispersion liquid;
spraying the dispersion liquid on one side of a proton exchange membrane, and drying to obtain the proton exchange membrane containing a water retention layer;
and preparing or assembling the catalytic layer and the gas diffusion layer of the proton exchange membrane containing the water retention layer to obtain the membrane electrode.
Optionally, the temperature of the drying is 70-100 ℃.
Optionally, the catalytic layer comprises an anode catalytic layer and a cathode catalytic layer, and the Pt loading of the anode catalytic layer is 0.05mg/cm 2 -0.4mg/cm 2 The Pt loading of the cathode catalytic layer is 0.2mg/cm 2 -0.4mg/cm 2 。
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
the water-retaining layer provided by the embodiment of the invention has the advantages that the effective water-retaining component is the super absorbent resin, and the super absorbent resin has more excellent hydrophilicity and water-retaining capacity compared with inorganic oxide and other high molecular polymers, can effectively strengthen the back diffusion of water generated by a cathode, can reduce the thickness of the water-retaining layer, and has good wetting effect on a proton exchange membrane and an anode catalytic layer while ensuring the proton conductivity, thereby realizing the high performance of a membrane electrode under the low-humidity operation condition.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a membrane electrode according to an embodiment of the present invention;
reference numerals: 1-proton exchange membrane, 2-water retention layer, 3-anode catalytic layer, 4-cathode catalytic layer, 5-anode gas diffusion layer and 6-cathode gas diffusion layer.
Detailed Description
The advantages and various effects of the present invention will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the invention, not to limit the invention.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Noun interpretation:
PEMFC: proton exchange membrane fuel cell proton exchange membrane fuel cell
MEA: membrane electrode assembly Membrane electrode
CL: catalyst layer
Nafion (r): erfluorosulfonic acid-PTFE copolymer, perfluorosulfonic acid-polytetrafluoroethylene copolymer
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
applicants found during the course of the invention that: the Catalytic Layer (CL) is an important component of the membrane electrode and is the main place where chemical reactions occur. In proton exchange membrane fuel cells, the cathode generates a large amount of water, and if the water generated by the cathode can be diffused from the cathode to the proton exchange membrane and the anode through a back diffusion process, the membrane electrode can be realized without external humidification. Therefore, the addition of a suitable substance to the anode catalytic layer accelerates the diffusion of water from the cathode to the anode is proposed. Jung et al have incorporated hydrophilic oxides such as silica into the catalytic layer to achieve self-humidification of the membrane electrode, and Liao et al have added water-retaining group-containing substances such as polyols and polysaccharides into the anode catalytic layer to achieve good cell performance of the MEA at low humidity. Although the self-humidification ability of the MEA can be achieved under low humidity conditions by adding some hydrophilic substances to the anode catalytic layer, the self-humidification ability of the PEMFC is improved, but at the same time, some problems are brought. Most hydrophilic substances are non-conductive, so that the addition of hydrophilic substances affects the electron conducting capacity of the anode catalytic layer, thereby increasing the charge transfer resistance of the MEA and resulting in a decrease in MEA performance. For example, by adding hydrophilic SiO to the catalytic layer 2 、TiO 2 、ZnO、Al 2 O 3 The water-retaining capacity of the membrane electrode is obviously improved by inorganic oxide nano particles or substances containing water-retaining groups such as polyalcohols, polysaccharides and the like; however, the water-retaining material is non-conductive or poor in conductivity, and the conductivity of the catalytic layer is affected after the water-retaining material is added, so that the charge transfer resistance of the MEA is increased, and the performance of the MEA is reduced.
In addition, some patents disclose catalyst coated membrane electrodes in which a water-retaining layer is added to the electrode structure, with the proposed water-retaining layer being interposed between the gas diffusion layer and the catalyst layer. The structure can retain water generated by the cell reaction, moisten the proton exchange resin in the proton exchange membrane and the catalyst layer, and ensure stable electric output of the fuel cell. However, because the water content in the water-retaining layer is high, the gas diffusion path from the gas diffusion layer to the anode catalytic layer is easily blocked, and the efficiency of gas transmission to the anode catalytic layer is affected, so that the performance of the MEA is reduced.
According to an exemplary embodiment of the present invention, there is provided a water-retaining layer, the water-retaining layer comprising: super absorbent resins and Nafion solution.
In some embodiments, the superabsorbent resin may be selected from at least one of a polyacrylate, a starch acrylate polymer, a starch-acrylonitrile graft copolymer, a polyacrylic acid-acrylamide, an acrylamide-acrylonitrile-acrylic acid.
Compared with inorganic oxide and other high molecular polymers, the super absorbent resin has more excellent hydrophilicity and water retention capacity, can effectively strengthen the back diffusion of water generated by a cathode, has good wetting effect on a proton exchange membrane and an anode catalytic layer, and ensures the performance of the MEA under low-humidity operation conditions.
In some embodiments, the mass ratio of the super absorbent resin to the Nafion ionomer in the Nafion solution is 5% to 30%:70% -95%; the mass ratio of the super absorbent resin to the Nafion ionomer includes, but is not limited to, 5% to 95%, 10% to 90%, 15% to 85%, 20% to 80%, 25% to 75%, 30% to 70%, etc.
The mass ratio of the super absorbent resin to the Nafion ionomer is controlled to be 5% -30%:70% -95% is to balance the water retention capacity and proton conduction capacity, and the excessive ratio results in too low Nafion content in the water retention layer, which is unfavorable for proton conduction, and too low water retention agent content, which is unfavorable for back diffusion of cathode water.
In some embodiments, the water-retaining layer material further includes a solvent comprising a mixture of water and isopropyl alcohol in a mass ratio of 1-3:1-5, including but not limited to 1:1, 1:3, 1:5, 2:1, 2:3, 2:5, 3:1, 3:2, 3:4, 3:5, etc.
Controlling the mass ratio of water to isopropanol to be 1-3:1-5 are to balance the solubility of the raw materials in the water-retaining layer and the volatility of the solution in the drying process, wherein water is mainly used for the dissolution of the water-retaining agent and the uniform dispersion of Nafion, isopropanol can realize the rapid volatilization of the solvent after the mixed system is sprayed on the membrane, so that the swelling problem of the proton exchange membrane is avoided, if the content of the isopropanol is too low, the volatilization rate of the solvent after the solution is sprayed on the membrane is too slow, the water-absorbing swelling of the proton exchange membrane is easily caused, and if the content of the water is too low, the dissolution of the water-retaining agent and the uniform dispersion of Nafion are not facilitated.
In some embodiments, the mass of Nafion ionomer in the super absorbent resin and Nafion solution is 1% -10% of the mass of the feedstock, and the mass of super absorbent resin and Nafion ionomer is 1%, 3%, 5%, 7%, 9% and 10% of the mass of the feedstock.
The reason for controlling the mass of the super absorbent resin and the Nafion ionomer to account for 1-10% of the mass of the raw materials is to ensure the dissolution of the super absorbent resin and the uniform dispersion of the Nafion under the condition of reaching a certain spraying efficiency, thereby obtaining a water-retaining layer with uniform components. The excessive value of the proportion can not realize the complete dissolution of the super absorbent resin and the uniform dispersion of Nafion, and the adverse effect of the excessively small proportion is that the mass fraction of the solution is too low, and the solution can reach a certain water retention layer thickness after being sprayed for many times, so that the spraying efficiency is reduced.
Generally, the mass concentration of the commercially available Nafion solution is 5% -20%, and the mass concentration of the Nafion solution includes but is not limited to: 5%, 10% and 20%, in other embodiments, those skilled in the art may choose other concentrations of Nafion solution according to the actual situation and needs.
In some embodiments, the thickness of the water-retaining layer is 0.5 μm-2 μm, including but not limited to 0.5 μm, 1 μm, 1.5 μm, and 2 μm.
The thickness of the water-retaining layer is controlled, the influence on the proton conduction rate between two adjacent layers can be reduced, the performance of the MEA is ensured, and if the thickness is too small, the water-retaining capacity can be insufficient.
In order to solve the problem that the water-retaining layer is between the gas diffusion layer and the catalyst layer, and the gas diffusion path of the easy-to-block gas diffusion layer to the anode catalytic layer is caused, the efficiency of gas transmission to the anode catalytic layer is affected, and therefore the performance of the MEA is reduced, the application also provides a membrane electrode.
According to another exemplary embodiment of the present invention, there is provided a membrane electrode comprising a water-retaining layer as described above.
In some embodiments, the membrane electrode further comprises a proton exchange membrane and an anode catalytic layer, the water retention layer being disposed between the proton exchange membrane and the anode catalytic layer.
In other embodiments, the water-retaining layer may be other water-retaining layers known to those skilled in the art, but the position of the water-retaining layer is disposed between the proton exchange membrane and the anode catalytic layer, so as to solve the problem of blocking the gas diffusion path from the gas diffusion layer to the anode catalytic layer.
The water-retaining agent super absorbent resin is prevented from being directly added into the anode catalytic layer or between the anode catalytic layer and the gas diffusion layer, so that the electron conduction and gas diffusion capacity of the anode are not influenced, and the performance of the MEA is ensured.
In this example, a commercial proton exchange membrane may be used, which may be a 15 μm membrane manufactured by America Corp or an 8 μm, 12 μm, 15 μm, 18 μm membrane manufactured by Golgi, america.
According to another exemplary embodiment of the present invention, there is provided a method for manufacturing a membrane electrode, the method including:
s1, mixing super absorbent resin and Nafion solution in a solvent to obtain a dispersion liquid;
specifically, the super absorbent resin and the Nafion solution are added into a mixed solvent of water and isopropanol, and after high-speed stirring, the super absorbent resin and the Nafion solution are uniformly dispersed by ultrasonic waves to obtain a dispersion liquid. Wherein the super absorbent resin is one or more of polyacrylate, starch acrylate polymer, starch-acrylonitrile grafting copolymer, polyacrylic acid-acrylamide and acrylamide-acrylonitrile-acrylic acid, and the mass fraction of Nafion solution is 5-20%. In the mixed solvent, the mass ratio of water to isopropanol is 3:1-1:5. In the dispersion liquid, the mass fraction of the mixture of the super absorbent resin and the Nafion in the dispersion liquid is 1-10%, and the mass ratio of the super absorbent resin in the mixture of the super absorbent resin and the Nafion is 5-30%. The stirring speed is 3000-10000r/min, and the stirring time is 10-30min. The ultrasonic power is 300-600W, and the ultrasonic dispersion time is 30-90min.
S2, spraying the dispersion liquid on one side of a proton exchange membrane, and drying to obtain the proton exchange membrane containing a water retention layer;
specifically, the commercial proton exchange membrane is fixed on a vacuum heating table after temperature rise, the dispersion liquid is sprayed on one side of the commercial proton exchange membrane, and a water-retaining layer is obtained after drying. Among these, commercial proton exchange membranes are 15 μm membranes produced by America Corp or 8 μm, 12 μm, 15 μm, 18 μm membranes produced by America Goer. The temperature of the spraying table top is 70-100 ℃. The thickness of the water-retaining layer is 0.5-2 μm.
S3, preparing or assembling the catalytic layer and the gas diffusion layer of the proton exchange membrane containing the water retention layer to obtain the membrane electrode.
Specifically, the preparation method comprises the steps of: adding Pt/C catalyst into mixed solution of Nafion and isopropanol, stirring, ultrasonic dispersing, spraying onto water-retaining layer side of proton exchange membrane, and taking as anode catalytic layer with Pt loading of 0.05-0.4mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Pt loading includes, but is not limited to: 0.05mg/cm 2 、0.1mg/cm 2 、0.15mg/cm 2 、0.2mg/cm 2 、0.25mg/cm 2 、0.30mg/cm 2 、0.35mg/cm 2 And 0.4mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Adding Pt/C catalyst into mixed solution of Nafion and isopropanol, stirring, ultrasonic dispersing, spraying onto the side of proton exchange membrane without water retention layer, and taking as cathode catalytic layer with Pt loading of 0.2-0.4mg/cm 2 Pt loading includes, but is not limited to: 0.2mg/cm 2 、0.25mg/cm 2 、0.30mg/cm 2 、0.35mg/cm 2 And 0.4mg/cm 2 Obtaining the CCM electrode. The Pt mass fraction of the Pt/C catalyst for the anode side is 20% -50%, including but not limited to 20%, 25%, 30%, 35%, 40%, 45% and 50%, and the cathodeThe mass fraction of Pt for the polar side Pt/C catalyst is 30% -70%, including but not limited to 30%, 40%, 50%, 60% and 70%.
The assembly of the diffusion layer is also included: the membrane electrode assembly for a fuel cell is obtained by sequentially assembling and hot-pressing the commercial gas diffusion layer and the prepared CCM electrode. The hot pressing pressure is 0.2-1.5MPa, and the hot pressing time is 30-180 s.
The water-retaining layer, the membrane electrode and the preparation method thereof of the present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
A method for preparing a membrane electrode, the method comprising:
s1, preparation of a water-retaining layer:
6mg of sodium polyacrylate and 480mg of 5wt.% Nafion solution were added to a mixed solvent containing 1000mg of water and 500mg of isopropanol, and after stirring for 30min at 3000r/min, the solution was dispersed by ultrasonic at 300W for 90min. Fixing the Kemu 15 mu m proton exchange membrane on a vacuum heating table with the temperature of 75 ℃, ultrasonically spraying the obtained dispersion liquid on one side of the proton exchange membrane, and drying to obtain a water-retaining layer with the thickness of 0.7 mu m.
S2, preparing a catalytic layer:
adding 30wt.% Pt/C catalyst into mixed solution of Nafion and isopropanol, stirring, ultrasonic dispersing uniformly, spraying onto one side of proton exchange membrane containing water retention layer, and taking as anode catalytic layer with Pt load of 0.1mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the 50wt.% Pt/C catalyst is added into the mixed solution of Nafion and isopropanol, stirred and dispersed evenly by ultrasound, and then sprayed on the side of the proton exchange membrane which does not contain a water retention layer, and the Pt loading is 0.4mg/cm as a cathode catalytic layer 2 Obtaining the CCM electrode.
S3, preparing a membrane electrode assembly:
and (3) sequentially assembling and hot-pressing the CCM electrode prepared in the step (2) and a commercial gas diffusion layer to obtain the membrane electrode assembly for the fuel cell. The hot pressing pressure is 0.2MPa, and the hot pressing time is 120s.
Example 2
A method for preparing a membrane electrode, the method comprising:
s1, preparation of a water-retaining layer:
13mg of starch-acrylonitrile graft copolymer and 491mg of 5wt.% Nafion solution were added to a mixed solvent containing 700mg of water and 700mg of isopropanol, and after stirring for 15min at 5000r/min, 500W was sonicated for 30min. And fixing the Goel 12 mu m proton exchange membrane on a vacuum heating table with the temperature of 80 ℃, ultrasonically spraying the obtained dispersion liquid on one side of the proton exchange membrane, and drying to obtain a water-retaining layer with the thickness of 0.9 mu m.
S2, preparing a catalytic layer:
adding 20wt.% Pt/C catalyst into mixed solution of Nafion and isopropanol, stirring, ultrasonic dispersing uniformly, spraying onto one side of proton exchange membrane containing water retention layer, and taking as anode catalytic layer with Pt load of 0.05mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Adding 60wt.% Pt/C catalyst into mixed solution of Nafion and isopropanol, stirring, ultrasonic dispersing uniformly, spraying onto one side of proton exchange membrane without water retention layer, and taking as cathode catalytic layer with Pt load of 0.3mg/cm 2 Obtaining the CCM electrode.
S3, preparing a membrane electrode assembly:
the membrane electrode assembly for a fuel cell is obtained by sequentially assembling and hot-pressing the commercial gas diffusion layer and the prepared CCM electrode. The hot pressing pressure is 0.5MPa, and the hot pressing time is 120s.
Example 3
A method for preparing a membrane electrode, the method comprising:
s1, preparation of a water-retaining layer:
7.3mg of acrylamide-acrylonitrile-acrylic acid and 288mg of 5wt.% Nafion solution were added to a mixed solvent containing 106mg of water and 319mg of isopropanol, and after stirring for 10min at 10000r/min, 400W was sonicated for 60min. The Goel 8 mu m proton exchange membrane is fixed on a vacuum heating table after temperature rise, the temperature of the heating table is 90 ℃, the obtained dispersion liquid is sprayed on one side of the proton exchange membrane in an ultrasonic mode, and a water-retaining layer with the thickness of 0.4 mu m is obtained after drying.
S2, preparing a catalytic layer:
50wt.% Pt/C catalyst is added into the mixed solution of Nafion and isopropanol, stirred and dispersed evenly by ultrasonic, and then sprayedTo the side of the proton exchange membrane containing the water retention layer, the Pt loading is 0.15mg/cm as the anode catalytic layer 2 The method comprises the steps of carrying out a first treatment on the surface of the 70wt.% Pt/C catalyst is added into the mixed solution of Nafion and isopropanol, stirred and dispersed evenly by ultrasound, and then sprayed on the side of the proton exchange membrane which does not contain a water retention layer, and the Pt loading is 0.25mg/cm as a cathode catalytic layer 2 Obtaining the CCM electrode.
S3, preparing a membrane electrode assembly:
the membrane electrode assembly for a fuel cell is obtained by sequentially assembling and hot-pressing the commercial gas diffusion layer and the prepared CCM electrode. The hot pressing pressure is 1MPa, and the hot pressing time is 30s.
Example 4
A method for preparing a membrane electrode, the method comprising:
s1, preparation of a water-retaining layer:
26mg of acrylamide-acrylonitrile-acrylic acid and 502mg of 5wt.% Nafion solution were added to a mixed solvent containing 3750mg of water and 3750 isopropanol, and after stirring for 10min at 8000r/min, 600W was sonicated for 30min. The Goel 8 mu m proton exchange membrane is fixed on a vacuum heating table after temperature rise, the temperature of the heating table is 90 ℃, the obtained dispersion liquid is sprayed on one side of the proton exchange membrane in an ultrasonic mode, and a water-retaining layer with the thickness of 1.4 mu m is obtained after drying.
S2, preparing a catalytic layer:
50wt.% Pt/C catalyst is added into the mixed solution of Nafion and isopropanol, stirred and dispersed evenly by ultrasonic, and then sprayed on one side of the proton exchange membrane containing the water retention layer to be used as an anode catalytic layer, wherein the Pt loading is 0.15mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the 70wt.% Pt/C catalyst is added into the mixed solution of Nafion and isopropanol, stirred and dispersed evenly by ultrasound, and then sprayed on the side of the proton exchange membrane which does not contain a water retention layer, and the Pt loading is 0.25mg/cm as a cathode catalytic layer 2 Obtaining the CCM electrode.
S3, preparing a membrane electrode assembly:
the membrane electrode assembly for a fuel cell is obtained by sequentially assembling and hot-pressing the commercial gas diffusion layer and the prepared CCM electrode. The hot pressing pressure is 1.5MPa, and the hot pressing time is 30s.
Comparative example 1
Referring to example 1, the difference is that the aqueous layer dispersion in step 1 is sprayed onto the commercial gas diffusion layer, with the aqueous layer in the MEA between the anode catalyst layer and the gas diffusion layer.
Comparative example 2
Referring to example 1, the difference is that the water retention agent is replaced with SiO in step 1 2 。
Comparative example 3
Referring to example 1, the difference is that the water retention agent is replaced with polyethylene glycol in step 1.
Comparative example 4
Referring to example 1, the difference is that the water-retaining agent is replaced with glucose in step 1.
Comparative example 5
Reference example 1 was made, except that no water-retaining agent was added in step 1.
Experimental example
The membrane electrodes prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance tests specifically including: under the condition of low humidity, the different membrane electrodes take hydrogen as fuel and air as oxidant, and the back pressure of the anode and the cathode is 250kPa abs The anode metering ratio was 1.5, the cathode metering ratio was 4.0, and the test results are shown in the following table.
As can be seen from the graph, the membrane electrode prepared by the method provided by the embodiment of the present invention has good performance, and the performance of the MEA with the water retention layer between the anode catalyst layer and the gas diffusion layer is lower than the performance of the MEA with the water retention layer between the proton exchange membrane and the anode catalyst layer as can be obtained by comparing the embodiment 1 with the comparison example 1; as can be obtained by comparing comparative examples 2 to 5 with example 1, the super absorbent resin has more excellent hydrophilicity and water retention capacity than the inorganic oxide and other high molecular polymers, and the addition of the super absorbent resin can improve the performance of the MEA under low humidity operation conditions.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) The effective water-retaining component of the water-retaining layer provided by the embodiment of the invention is super absorbent resin, and the super absorbent resin has better hydrophilicity and water-retaining capacity compared with inorganic oxide and other high molecular polymers, can effectively strengthen the back diffusion of water generated by a cathode, and has good wetting effect on a proton exchange membrane and an anode catalytic layer;
(2) The membrane electrode provided by the embodiment of the invention does not directly add the water-retaining agent super absorbent resin in the anode catalytic layer or between the anode catalytic layer and the gas diffusion layer, so that the electron conduction and the gas diffusion capacity of the anode are not affected;
(3) The water-retaining layer provided by the embodiment of the invention has excellent water-retaining capacity, and can effectively reduce the thickness of the water-retaining layer, thereby reducing the influence on the proton conduction rate between the catalytic layer and the proton exchange membrane;
(4) The membrane electrode provided by the embodiment of the invention ensures the performance of the MEA while realizing the self-humidifying operation condition of the MEA.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (7)
1. The membrane electrode is characterized by comprising a water-retaining layer, a proton exchange membrane and an anode catalytic layer, wherein the water-retaining layer is arranged between the proton exchange membrane and the anode catalytic layer, and raw materials of the water-retaining layer comprise: the high-water-absorptivity resin, nafion solution and solvent, wherein the mass ratio of Nafion ionomer in the Gao Xishui resin to the Nafion solution is 5% -30% to 70% -95%, the mass ratio of Nafion ionomer in the Gao Xishui resin to the Nafion solution is 1% -10% of the mass of the raw materials, the thickness of the water-retaining layer is 0.5-1 μm, the mass concentration of the Nafion solution is 5% -20%, the solvent is a mixture of water and isopropanol, and the mass ratio of water to isopropanol is 1-3:1-5.
2. The membrane electrode of claim 1, wherein the superabsorbent resin comprises at least one of a polyacrylate, a starch acrylate polymer, a starch-acrylonitrile graft copolymer, a polyacrylic acid-acrylamide, an acrylamide-acrylonitrile-acrylic acid.
3. The membrane electrode of claim 1, wherein the water-retention layer is applied to the proton exchange membrane.
4. The membrane electrode of claim 1, wherein the proton exchange membrane has a thickness of 5 μm to 20 μm.
5. A method of producing the membrane electrode as claimed in any one of claims 1 to 4, characterized in that the method comprises:
mixing high water absorption resin and Nafion solution in a solvent to obtain dispersion liquid;
spraying the dispersion liquid on one side of a proton exchange membrane, and drying to obtain the proton exchange membrane containing a water retention layer;
and preparing or assembling the catalytic layer and the gas diffusion layer of the proton exchange membrane containing the water retention layer to obtain the membrane electrode.
6. The method for producing a membrane electrode according to claim 5, wherein the temperature of the drying is 70 ℃ to 100 ℃.
7. The method for producing a membrane electrode according to claim 5, wherein the catalyst layer comprises an anode catalyst layer and a cathode catalyst layer, and the Pt loading of the anode catalyst layer is 0.05mg/cm 2 -0.4mg/cm 2 The Pt loading of the cathode catalytic layer is 0.2mg/cm 2 -0.4mg/cm 2 。
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