CN115000420B - Cathode catalytic membrane, membrane electrode, preparation method of membrane electrode and fuel cell - Google Patents
Cathode catalytic membrane, membrane electrode, preparation method of membrane electrode and fuel cellInfo
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- CN115000420B CN115000420B CN202210534777.0A CN202210534777A CN115000420B CN 115000420 B CN115000420 B CN 115000420B CN 202210534777 A CN202210534777 A CN 202210534777A CN 115000420 B CN115000420 B CN 115000420B
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Abstract
The invention relates to a cathode catalytic membrane, a membrane electrode, a preparation method of the membrane electrode and a fuel cell. In the preparation method of the membrane electrode, the cathode catalytic membrane group comprises n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity, n is an integer not less than 2, and the catalyst in the cathode catalytic membrane comprises a carbon-supported metal catalyst; immersing the n layers of cathode catalytic films in sulfuric acid for corrosion treatment respectively, and along with the gradual increase of the hydrophobicity and the porosity of the cathode catalytic films, obtaining n layers of cathode catalytic films after corrosion treatment, wherein the longer the time for each corrosion treatment and/or the higher the concentration of sulfuric acid adopted by each corrosion treatment are: setting an anode catalytic layer on one side of a proton exchange membrane, and sequentially setting n layers of cathode catalytic membranes after corrosion treatment on the other side of the proton exchange membrane according to the rule of increasing hydrophobicity and porosity step by step to obtain a membrane electrode. The preparation method of the membrane electrode can improve the drainage capacity and the gas transportation capacity of the prepared membrane electrode.
Description
Technical Field
The invention relates to the technical field of battery preparation, in particular to a cathode catalytic membrane, a membrane electrode, a preparation method of the membrane electrode and a fuel cell.
Background
Along with the increasingly prominent contradiction between social and economic development and energy shortage and environmental pollution, the development of green energy becomes more and more a global focus of attention. The fuel cell is a device for directly converting chemical energy of fuel into electric energy, has high energy density and energy conversion efficiency, is low in pollution, is an ideal power supply in the future, and has become an important break for global automobile and energy industry transformation and upgrading when developing fuel cell automobiles, and the fuel cell can take hydrogen-rich gas such as natural gas and the like as fuel, so that the emission of carbon dioxide is reduced by more than 40% than a thermal process, and has important significance for relieving greenhouse effect.
The membrane fuel cell mainly comprises a proton exchange membrane, a cathode/anode catalytic layer, a cathode/anode gas diffusion layer, a cathode/anode frame and the like, wherein the proton exchange membrane and the cathode/anode catalytic layer form a membrane electrode which is a working place for generating chemical reaction and electric energy and plays a main role in the performance and service life of the fuel cell, and the catalytic layer is a core place for electrochemical reaction and plays a key role in the process of converting chemical energy into electric energy. The cathode catalytic membrane is a place where protons, electrons and oxygen produce water under the catalysis, the process needs to ensure sufficient oxygen supply to enable the reaction to be continuous, and meanwhile, if a large amount of water is produced and is not discharged out of the cathode catalytic membrane rapidly, the phenomenon of blocking the cathode catalytic membrane can be caused, and the gas transmission is influenced, so that the performance of a membrane electrode is influenced. However, the drainage capacity and gas transport capacity of the conventional membrane electrode are limited, and cannot meet the requirements of people on the higher and higher performance of the proton exchange membrane fuel cell.
Accordingly, the conventional technology has yet to be improved.
Disclosure of Invention
Based on the above, the invention provides a cathode catalytic membrane, a membrane electrode, a preparation method thereof and a fuel cell, wherein the preparation method of the membrane electrode can improve the drainage capacity and the gas transportation capacity of the prepared membrane electrode.
In one aspect of the present application, a method for preparing a membrane electrode is provided, which is characterized by comprising the steps of:
Providing an anode catalytic layer, a proton exchange membrane and a cathode catalytic membrane group, wherein the cathode catalytic membrane group comprises n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity, n is an integer not less than 2, and a catalyst in the cathode catalytic membranes comprises a carbon-supported metal catalyst;
Immersing the n layers of cathode catalytic films in sulfuric acid for corrosion treatment respectively, and as the hydrophobicity and the porosity of the cathode catalytic films are gradually increased, the longer the corrosion treatment is carried out each time and/or the higher the concentration of the sulfuric acid adopted by the corrosion treatment is carried out each time, so as to obtain the n layers of cathode catalytic films after the corrosion treatment:
and arranging the anode catalytic layer on one side of the proton exchange membrane, and arranging the n cathode catalytic membranes subjected to corrosion treatment on the other side of the proton exchange membrane in sequence according to the rule of increasing hydrophobicity and porosity step by step to obtain a membrane electrode.
In some of these embodiments, the minimum concentration of the sulfuric acid employed in the corrosion treatment is 10wt% to 20wt%; and/or
The minimum time for the etching treatment was 1h.
In some of these embodiments, the temperature of the etching process is from 40 ℃ to 60 ℃.
In some embodiments, n is 3, and the cathode catalytic membrane group includes a first cathode catalytic membrane, a second cathode catalytic membrane, and a third cathode catalytic membrane having progressively higher hydrophobicity and porosity.
In some embodiments, when the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are respectively subjected to the corrosion treatment, the concentration of the sulfuric acid adopted in the corrosion treatment is respectively 10wt% to 20wt%, 20wt% to 30wt%, and 30wt% to 40wt%.
In some embodiments, when the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are respectively subjected to the corrosion treatment, the time of the corrosion treatment is 1h to 2h, 2h to 3h and 3h to 5h.
In some of these embodiments, the mass ratio of the added hydrophobizing agent to the carbon support in the catalyst is stepwise increased when the first, second and third cathode catalytic films are prepared, so that the hydrophobicity of the prepared first, second and third cathode catalytic films is stepwise increased; and/or
When the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are prepared, the mass ratio of the added pore-forming agent to the carbon carrier in the catalyst is gradually increased, so that the porosities of the prepared first cathode catalytic film, second cathode catalytic film and third cathode catalytic film are gradually increased.
In some of these embodiments, the first cathode catalytic film is prepared using a mass ratio of pore-forming agent to carbon support in the catalyst of (1-3): (9-7), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (0.5-1.5): (9.5 to 8.5); and/or
When the second cathode catalytic film is prepared, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (3.1-6): (7-4), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (1.5-4.5): (8.5-5.5); and/or
When the third cathode catalytic film is prepared, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (6.1-10): (4-1), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (4.5-5.5): (5.5-4.5).
In some of these embodiments, the hydrophobic agent is selected from one or more of activated carbon, PTFE emulsion, polysiloxane; and/or
The pore-forming agent is selected from one or more of ammonium oxalate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, nano PTFE particles, methylcellulose, nano activated carbon and nano carbon fiber tubes.
In another aspect of the present invention, there is provided a method for preparing a cathode catalytic film, comprising the steps of:
Mixing a catalyst, an ionomer and a solvent to obtain a catalyst slurry; the catalyst comprises a carbon supported metal catalyst;
Coating and drying the catalyst slurry to obtain a catalyst prefabricated film;
And immersing the catalyst prefabricated film in sulfuric acid for corrosion treatment to obtain the cathode catalytic film.
In some embodiments, the concentration of the sulfuric acid is 10wt% to 40wt% for a period of time ranging from 1h to 6h.
In yet another aspect of the present invention, there is provided a cathode catalytic membrane prepared by the method of preparing a cathode catalytic membrane as described above.
In yet another aspect of the invention, there is provided a membrane electrode made using the method of making a membrane electrode as described above or comprising a cathode catalytic membrane as described above.
In yet another aspect of the present invention, there is provided a fuel cell comprising a membrane electrode as described above.
In the preparation method of the membrane electrode, the n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity are immersed in sulfuric acid for corrosion treatment respectively, the catalyst in the cathode catalytic membranes comprises a carbon-supported metal catalyst, after the sulfuric acid treatment, oxygen-containing functional groups with high hydrophobicity are generated, and meanwhile, the configuration of a carbon negative carrier in the catalyst is changed, so that the hydrophobicity and the porosity of the cathode catalytic membranes are improved, and the gradually increased hydrophobicity and the porosity of the cathode catalytic membranes are controlled, the longer the time of each corrosion treatment and/or the higher the concentration of sulfuric acid adopted by each corrosion treatment are controlled, so that the hydrophobicity and the porosity of the cathode catalytic membranes after the corrosion treatment still have a gradually increased rule, and then the n layers of cathode catalytic membranes after the corrosion treatment are sequentially arranged on the other side of the proton exchange membrane according to the gradually increased rule of the hydrophobicity and the porosity, so that the membrane electrode has the gradient increased hydrophobicity and the porosity, and the cathode catalytic membranes in the outward direction are provided with the gradient, and even if more accumulated water is more satisfied in the drainage process, the drainage force is still provided by the gradient, the drainage resistance is not increased, and the drainage resistance is not only provided, but also the drainage resistance is increased, but the drainage resistance is not increased, and the drainage resistance is provided.
In the preparation method of the cathode catalytic membrane, a catalyst, an ionomer and a solvent are mixed to obtain a catalyst slurry; then coating and drying the catalyst slurry to obtain a catalyst prefabricated film, soaking the catalyst prefabricated film in sulfuric acid for corrosion treatment respectively, wherein the catalyst in the cathode catalytic film comprises a carbon-supported metal catalyst, and after the catalyst is subjected to sulfuric acid treatment, oxygen-containing functional groups with high hydrophobicity are generated, and meanwhile, the configuration of a carbon carrier in the catalyst is changed, so that the hydrophobicity and the porosity of the cathode catalytic film are improved.
Drawings
Fig. 1 is a structural view of a fuel cell in an embodiment;
FIG. 2 is a graph showing the power density curves of the fuel cell prepared in example 1 versus that of a blank fuel cell;
FIG. 3 is a graph showing the power density curves of the fuel cell and the blank fuel cell obtained in example 2;
FIG. 4 is a graph showing the power density curves of the fuel cell prepared in example 3 versus that of a blank fuel cell;
Fig. 5 is a graph showing the power density curves of the fuel cell prepared in example 4 and a blank fuel cell.
Reference numerals illustrate:
1a fuel cell; 10 proton exchange membrane; 20 cathode catalytic membrane group; a 30 cathode diffusion layer; 40 anode catalytic layer; 50 anode diffusion layer; a first cathode catalytic membrane 21; 22a second cathode catalytic membrane; and 23 a third cathode catalytic membrane.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. Preferred embodiments of the invention are given in the detailed description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
As described in the background, conventional membrane electrodes have limited drainage and gas transport capabilities, and the present inventors have found that: in the conventional technology, in order to increase the hydrophobicity or the porosity of the cathode catalytic layer, a functional additive is often required to be added, for example, a hydrophobic agent is required to be added to increase the hydrophobicity, and a pore-forming agent is required to be added to increase the porosity, but in order to maintain the catalytic efficiency and the activity of the cathode catalytic layer, the addition amount of the functional additive such as the hydrophobic agent and the pore-forming agent is limited, so that the capability of increasing the hydrophobicity or the porosity of the cathode catalytic layer is limited. The technical proposal of the application which can simultaneously improve the hydrophobicity or the porosity of the cathode catalytic layer is obtained by the technical personnel of the application after a great deal of experimental study. The specific technical scheme is as follows.
An embodiment of the present invention provides a method for preparing a cathode catalytic film, which includes the following steps S10 to S30.
Step S10, mixing a catalyst, an ionomer and a solvent to obtain a catalyst slurry; the catalyst comprises a carbon supported metal catalyst.
And step S20, coating and drying the catalyst slurry to obtain the catalyst prefabricated film.
And step S30, immersing the catalyst prefabricated film in sulfuric acid for corrosion treatment to obtain the cathode catalytic film.
In the preparation method of the cathode catalytic membrane, a catalyst, an ionomer and a solvent are mixed to obtain a catalyst slurry; then coating and drying the catalyst slurry to obtain a catalyst prefabricated film, soaking the catalyst prefabricated film in sulfuric acid for corrosion treatment respectively, wherein the catalyst in the cathode catalytic film comprises a carbon-supported metal catalyst, and after the catalyst is subjected to sulfuric acid treatment, oxygen-containing functional groups with high hydrophobicity are generated, and meanwhile, the configuration of a carbon carrier in the catalyst is changed, so that the hydrophobicity and the porosity of the cathode catalytic film are improved.
In some embodiments, the concentration of the sulfuric acid is 10wt% to 40wt% for 1h to 6h.
It will be appreciated that the above-mentioned sulfuric acid is added in the form of an aqueous sulfuric acid solution.
The carbon-supported metal catalyst includes a carbon support and a metal supported on the carbon support. In some of these embodiments, the catalyst is a Pt/C catalyst or a Pt-Co/C catalyst.
In some of these embodiments, the ionomer is a perfluorosulfonic acid resin.
In some of these embodiments, the ionomer is added as an ionomer solution having a mass fraction of 5wt% to 20wt%.
In some embodiments, the solvent is water or an organic solvent selected from at least one of n-propanol, isopropanol, ethanol, and ethyl acetate.
Further, the mass ratio of the catalyst to water is 1: (30-90); the mass ratio of water to organic solvent is (1-10): (10-1).
In some of these embodiments, the mass ratio of ionomer to carbon support in the catalyst is (0.7 to 1.1): 1.
In some of these embodiments, the etching process is performed in a small hole mold having a lattice structure.
In some embodiments, in step S30, the method further includes a step of washing and drying the cathode catalytic film after the corrosion treatment.
In some of these embodiments, the drying temperature is 80 ℃ to 110 ℃.
In some embodiments, the water wash is performed with deionized water for a period of time ranging from 10 minutes to 60 minutes. To remove sulfuric acid supported on the cathode catalytic membrane.
In one embodiment of the present invention, a method for preparing a membrane electrode is provided, which includes the following steps S40 to S60.
Step S40, providing an anode catalytic layer, a proton exchange membrane and a cathode catalytic membrane group, wherein the cathode catalytic membrane group comprises n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity, n is an integer not less than 2, and the catalyst in the cathode catalytic membranes comprises a carbon-supported metal catalyst.
And S50, immersing the n layers of cathode catalytic films in sulfuric acid for corrosion treatment respectively, wherein the hydrophobicity and the porosity of the cathode catalytic films are gradually increased, and the corrosion treatment time is longer each time and/or the concentration of sulfuric acid adopted by the corrosion treatment is higher each time, so that the n layers of cathode catalytic films after the corrosion treatment are obtained.
And step S60, arranging the anode catalytic layer on one side of the proton exchange membrane, and arranging the n layers of cathode catalytic membranes after corrosion treatment on the other side of the proton exchange membrane in sequence according to the rule of increasing hydrophobicity and porosity step by step to obtain the membrane electrode.
In the preparation method of the membrane electrode, the n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity are immersed in sulfuric acid for corrosion treatment respectively, the catalyst in the cathode catalytic membranes comprises a carbon-supported metal catalyst, after the sulfuric acid treatment, oxygen-containing functional groups with high hydrophobicity are generated, and meanwhile, the configuration of a carbon-supported carrier in the catalyst is changed, so that the hydrophobicity and the porosity of the cathode catalytic membranes are improved, and the gradually increased hydrophobicity and the porosity of the cathode catalytic membranes are controlled, the longer the time of each corrosion treatment and/or the higher the concentration of sulfuric acid adopted by each corrosion treatment are controlled, so that the hydrophobicity and the porosity of the n layers of cathode catalytic membranes after the corrosion treatment still have a rule of gradually increasing, and then the n layers of cathode catalytic membranes after the corrosion treatment are sequentially arranged on the other side of the proton exchange membrane according to the rule of gradually increasing the hydrophobicity and the porosity of the cathode catalytic membranes, so that the cathode catalytic membranes in the outward direction of the membrane electrode have increased hydrophobicity and the porosity, and in the drainage process, the drainage force of the cathode electrode is not only increased, but also provided by the gradient of the drainage gas, even if the drainage force of the cathode catalytic membranes is more water is increased, and the drainage force is not provided.
It can be understood that in the step S50, when the n-layer cathode catalytic film is subjected to corrosion treatment, the hydrophobicity and the porosity of the cathode catalytic film are higher, and correspondingly, the concentration of sulfuric acid adopted in the corrosion treatment is higher or the treatment time is longer, so that the hydrophobicity and the porosity of the n-layer cathode catalytic film after the corrosion treatment still have a rule of increasing step by step.
In some of these embodiments, the metal in the carbon supported metal catalyst comprises Pt.
In some of these embodiments, the carbon supported metal catalyst may be a Pt/C catalyst or a Pt-Co/C catalyst.
Specifically, the microscopic morphology of the Pt/C catalyst may be at least one of a spherical particle, a nanowire structure, a nanowarfare array structure, a core-shell structure, and an octahedral structure.
In some of these embodiments, the corrosion treatment employs sulfuric acid at a minimum concentration of 10wt% to 20wt% in step S50.
In some of these embodiments, in step S50, the minimum time for the etching process is 1h.
In some of these embodiments, the temperature of the etching process is 40-60 ℃ in step S50.
In a specific example, in step S50, the temperature at which each etching process is performed is controlled to be the same.
In some of these embodiments, n is 2, 3, 4, 5, 6, or 7.
In some of these embodiments, n is 3 and the cathode catalytic membrane group includes a first cathode catalytic membrane, a second cathode catalytic membrane, and a third cathode catalytic membrane having progressively higher hydrophobicity and porosity.
In some embodiments, in step S50, when the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are respectively subjected to corrosion treatment, the concentration of sulfuric acid adopted in the corrosion treatment is respectively 10wt% to 20wt%, 20wt% to 30wt%, and 30wt% to 40wt%.
In some embodiments, in step S50, when the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are respectively subjected to corrosion treatment, the corrosion treatment time is 1h to 2h, 2h to 3h and 3h to 5h.
In step S30, "n layers of cathode catalytic films having progressively higher hydrophobicity and porosity" means that each layer of cathode catalytic film has different hydrophobicity and different porosity, and the cathode catalytic films having different hydrophobicity and porosity may be combined or self-made in the prior art. In the step S60, the n cathode catalytic membranes after the corrosion treatment are sequentially disposed on the other side of the proton exchange membrane, and the hydrophobicity and the porosity of the n cathode catalytic membranes after the corrosion treatment are sequentially disposed according to the rule that the hydrophobicity and the porosity of the n cathode catalytic membranes after the corrosion treatment are gradually increased, that is, in the direction of outward radiation of the proton exchange membrane, the hydrophobicity and the porosity of the outer cathode catalytic membrane are higher than those of the inner cathode catalytic membrane. For example, the hydrophobicity and the porosity of the first cathode catalytic membrane, the second cathode catalytic membrane and the third cathode catalytic membrane after corrosion treatment are gradually increased, and then the first cathode catalytic membrane, the second cathode catalytic membrane and the third cathode catalytic membrane after corrosion treatment are sequentially arranged on the other side of the proton exchange membrane.
In some embodiments, the mass ratio of the added hydrophobizing agent to the carbon support in the catalyst is gradually increased when the first, second and third cathode catalytic films are prepared, so that the hydrophobicity of the prepared first, second and third cathode catalytic films is gradually increased.
In some embodiments, the mass ratio of pore formers to carbon support in the catalyst is incrementally increased as the first, second, and third cathode catalytic films are prepared, such that the porosities of the first, second, and third cathode catalytic films are incrementally increased.
Further, when preparing the first cathode catalytic film, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (1-3): (9-7), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (0.5-1.5): (9.5 to 8.5).
Further, when preparing the second cathode catalytic film, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (3.1-6): (7-4), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (1.5-4.5): (8.5-5.5).
Further, when preparing the third cathode catalytic film, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (6.1-10): (4-1), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (4.5-5.5): (5.5-4.5).
In some of these embodiments, the hydrophobic agent is selected from one or more of activated carbon, PTFE emulsion, polysiloxane.
In some of these embodiments, the pore-forming agent is selected from one or more of ammonium oxalate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, nano PTFE particles, methylcellulose, nano activated carbon, and nano carbon fiber tubes.
The ammonium oxalate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate and the like are decomposed to form holes, and the nano PTFE particles, methyl cellulose, nano activated carbon or nano carbon fiber tubes and the like are formed into holes through special pore structures.
In some embodiments, the anode catalytic layer is a single catalytic layer. Further, the catalyst of the anode catalytic layer is a supported metal catalyst, specifically at least one of a Pt/C catalyst and a Pt-Co/C catalyst.
In some of these embodiments, the anode catalytic layer has a platinum loading of 0.05mg/cm 2～0.1mg/cm2; the total platinum loading of the n-layer cathode catalytic film after the corrosion treatment was 0.2cm 2～0.4mg/cm2.
The primary function of the proton exchange membrane is to separate the oxidant from the reductant and conduct ions, and proton exchange membranes commonly used in the art can be used.
In a specific example, the proton exchange membrane is selected from Nafion112 or Nafion119.
In yet another embodiment of the present invention, there is provided a membrane electrode made by the method of making a membrane electrode as described above or comprising a cathode catalytic membrane as described above.
The membrane electrode has high drainage and gas transportation capacity and high activity.
In yet another embodiment of the present invention, a fuel cell is provided that includes a membrane electrode as described above.
The membrane electrode has high drainage and gas transportation capacity and high activity, and can improve the power density of the fuel cell.
In some embodiments, the fuel cell further comprises a diffusion layer and an electrode frame.
Specifically, the diffusion layer comprises a cathode diffusion layer and an anode diffusion layer, the cathode diffusion layer is arranged on one side of the cathode catalytic membrane far away from the proton exchange membrane, and the anode diffusion layer is arranged on one side of the anode catalytic membrane far away from the proton exchange membrane; the electrode frame includes a cathode frame and an anode frame.
Further, referring to fig. 1, in the structure of the fuel cell 1, a proton exchange membrane 10 is used as a starting point, a cathode catalytic membrane group 20 and a cathode diffusion layer 30 are sequentially arranged on one side of the proton exchange membrane 10, and an anode catalytic layer 40 and an anode diffusion layer 50 are sequentially arranged on the other side of the proton exchange membrane; the cathode catalytic membrane group 20 includes a first cathode catalytic membrane 21, a second cathode catalytic membrane 22, and a third cathode catalytic membrane 23, which are progressively increased in hydrophobicity and porosity after the etching treatment.
The invention will be described in connection with specific embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims outline the scope of the invention, and those skilled in the art, guided by the inventive concept, will appreciate that certain changes made to the embodiments of the invention will be covered by the spirit and scope of the appended claims.
The following are specific examples.
The catalysts in the following examples and comparative examples were Pt/C catalysts with a Pt content of commercial JM 9100%, ionomer solution was model D520 from Dupont, nafion112 commercial proton membrane, gas diffusion layer was produced by Shanghelsen electric, other chemicals were all from national pharmaceutical chemicals and ala Ding Huaxue reagent.
Example 1
(1) 0.10G of Pt/C catalyst with the platinum content of 60wt percent is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent Nafion solution are added, ultrasonic treatment is carried out for 2 hours at the temperature of 10 ℃ to obtain anode catalyst slurry which is uniformly dispersed, the anode catalyst slurry is sprayed on one surface of a proton exchange membrane, and the anode catalyst slurry is dried at the temperature of 100 ℃ to form an anode catalyst layer on the surface of the proton exchange membrane.
(2) Weighing 0.10g of Pt/C catalyst with the platinum content of 60wt%, adding 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt% Nafion solution, carrying out ultrasonic treatment at the temperature of 10 ℃ for 2 hours, then adding 0.01g of ammonium bicarbonate and 0.02g of 20wt% PTFE emulsion, continuing to keep ultrasonic treatment at the temperature of 10 ℃ for 2 hours to obtain first cathode catalyst slurry, spraying the first cathode catalyst slurry onto one surface, far away from an anode catalyst layer, of a commercial proton exchange membrane, and drying at the temperature of 100 ℃ to prepare a first cathode catalytic prefabricated membrane; then fixing by a small hole mould with a lattice structure, adding a sulfuric acid solution with the concentration of 15wt% into the mould to infiltrate the first cathode catalytic prefabricated film, corroding at 50 ℃ for 1 hour, washing with deionized water for 30 minutes, drying at 100 ℃ again to form the first cathode catalytic film, and testing the water contact angle and the porosity of the first cathode catalytic film, wherein the specific results are shown in Table 1.
(3) Weighing 0.10g of Pt/C catalyst with the platinum content of 60wt%, adding 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt% Nafion solution, carrying out ultrasonic treatment at the temperature of 10 ℃ for 2 hours, then adding 0.04g of ammonium bicarbonate and 0.09g of 20wt% PTFE emulsion, continuously keeping ultrasonic treatment at the temperature of 10 ℃ for 2 hours to obtain second catalyst slurry, spraying the second catalyst slurry onto the surface of the first cathode catalyst film far away from the proton exchange film, and drying at the temperature of 100 ℃ to prepare a second cathode catalyst prefabricated film; then fixing by a small hole mould with a lattice structure, adding 25% sulfuric acid solution with mass concentration into the mould to infiltrate a second cathode catalytic prefabricated film, corroding at 50 ℃ for 3 hours, washing with deionized water for 30 minutes, drying at 100 ℃ again to form a second cathode catalytic film, and testing the water contact angle and the porosity of the second cathode catalytic film, wherein the specific results are shown in Table 1.
(4) Weighing 0.10g of Pt/C catalyst with the platinum content of 60wt%, adding 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt% Nafion solution, carrying out ultrasonic treatment at the temperature of 10 ℃ for 2 hours, then adding 0.16g of ammonium bicarbonate and 0.20g of 20wt% PTFE emulsion, continuously keeping ultrasonic treatment at the temperature of 10 ℃ for 2 hours to obtain third catalyst slurry, spraying the third catalyst slurry onto the surface of the second cathode catalyst film far away from the first cathode catalyst film, drying at the temperature of 100 ℃ to prepare a third cathode catalyst prefabricated film, fixing the third cathode catalyst prefabricated film through a small hole die with a lattice structure, adding a sulfuric acid solution with the mass concentration of 35% into the die to infiltrate the third cathode catalyst prefabricated film, carrying out corrosion treatment at the temperature of 50 ℃ for 3 hours, then washing with deionized water for 30 minutes, and drying at the temperature of 100 ℃ again to form the third cathode catalyst film, thus obtaining the membrane electrode. And the third cathode catalytic film was tested for water contact angle and porosity, and specific results are shown in table 1.
(5) The prepared membrane electrode and the gas diffusion layer are assembled and packaged by an electrode frame to obtain the fuel cell, and the specific structure is shown in fig. 1.
Simultaneously preparing a blank fuel cell, which comprises the following steps:
1. 0.10g of Pt/C catalyst with the platinum content of 60wt percent is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent Nafion solution are added, ultrasonic treatment is carried out for 2 hours at the temperature of 10 ℃ to obtain anode catalyst slurry which is uniformly dispersed, the anode catalyst slurry is sprayed on one surface of a proton exchange membrane, and the anode catalyst slurry is dried at the temperature of 100 ℃ to form an anode catalyst layer on the surface of the proton exchange membrane.
2. 0.10G of Pt/C catalyst with 60wt percent of platinum content is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent of Nafion solution are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours, then 0.01g of ammonium bicarbonate and 0.02g of 20wt percent of PTFE emulsion are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours continuously, a first cathode catalyst slurry is obtained, and the first cathode catalyst slurry is sprayed on one surface of a commercial proton exchange membrane far away from an anode catalyst layer to form a first cathode catalyst membrane.
And (3) repeating the step (1) twice to form a second cathode catalytic film and a third cathode catalytic film respectively, and then assembling the second cathode catalytic film and the third cathode catalytic film with a gas diffusion layer and packaging the gas diffusion layer by using an electrode frame to obtain the blank fuel cell.
(6) The power density of the fuel cell and the blank fuel cell is tested, and the test is referred to the test method of the 5 th part membrane electrode of the GBT20042.5-2009 proton exchange membrane fuel cell, the power density curve is shown in figure 2, wherein A is the power density curve of the blank fuel cell, a is the voltage curve of the blank fuel cell, B is the power density curve of the fuel cell prepared in example 1, B is the voltage curve of the fuel cell prepared in example 1, and the maximum power density result is shown in table 1.
Example 2
Example 2 is substantially the same as example 1, except that: the mass of 20wt% PTFE emulsion in step (2) was 0.2g in example 2, and the mass of 20wt% PTFE emulsion in step (4) was 0.02g.
The remaining steps and conditions were the same as in example 1. The power density curve of the fuel cell is shown in fig. 3, wherein C is the power density curve of the fuel cell prepared in example 2, C is the voltage curve of the fuel cell prepared in example 2, and the maximum power density results are shown in table 1.
Example 3
Example 3 is substantially the same as example 1, except that: the mass of ammonium bicarbonate in step (2) in example 3 was 0.16g, the time of the etching treatment in step (3) was 3 hours, and the mass of ammonium bicarbonate in step (4) was 0.01g.
The remaining steps and conditions were the same as in example 1. The power density curve of the fuel cell is shown in fig. 4, wherein D is the power density curve of the fuel cell prepared in example 3, D is the voltage curve of the fuel cell prepared in example 3, and the maximum power density results are shown in table 1.
Example 4
Example 4 is substantially the same as example 1, except that: in example 4, the mass of ammonium bicarbonate in step (2) was 0.16g, the mass of 20wt% PTFE emulsion was 0.2g, the time of the etching treatment in step (3) was 3 hours, the mass of ammonium bicarbonate in step (4) was 0.01g, and the mass of 20wt% PTFE emulsion was 0.02g.
The remaining steps and conditions were the same as in example 1. The power density curve of the fuel cell is shown in fig. 5, wherein E is the power density curve of the fuel cell prepared in example 4, E is the voltage curve of the fuel cell prepared in example 4, and the maximum power density results are shown in table 1.
Comparative example 1
(1) 0.10G of Pt/C catalyst with the platinum content of 60wt percent is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent Nafion solution are added, ultrasonic treatment is carried out for 2 hours at the temperature of 10 ℃ to obtain anode catalyst slurry which is uniformly dispersed, the anode catalyst slurry is sprayed on one surface of a proton exchange membrane, and the anode catalyst slurry is dried at the temperature of 100 ℃ to form an anode catalyst layer on the surface of the proton exchange membrane.
(2) 0.10G of Pt/C catalyst with 60wt percent of platinum content is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent of Nafion solution are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours, then 0.01g of ammonium bicarbonate and 0.02g of 20wt percent of PTFE emulsion are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours continuously, a first cathode catalyst slurry is obtained, the first cathode catalyst slurry is sprayed on one surface of a commercial proton exchange membrane far away from an anode catalyst layer, the first cathode catalyst film is formed by drying at 100 ℃, and the water contact angle and the porosity of the first cathode catalyst film are tested, and specific results are shown in Table 1.
(3) 0.10G of Pt/C catalyst with 60wt% of platinum content is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt% of Nafion solution are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours, then 0.04g of ammonium bicarbonate and 0.09g of 20wt% of PTFE emulsion are added, ultrasonic treatment is carried out at 10 ℃ for 2 hours continuously, second catalyst slurry is obtained, the second catalyst slurry is sprayed on the surface of the first cathode catalyst film far away from the proton exchange film, the second cathode catalyst film is formed by drying at 100 ℃, and the water contact angle, namely the porosity of the second cathode catalyst film is tested, and specific results are shown in table 1.
(4) 0.10G of Pt/C catalyst with the platinum content of 60wt percent is weighed, 5.20g of water, 8.80g of isopropanol and 0.80g of 5wt percent Nafion solution are added, ultrasonic treatment is carried out at the temperature of 10 ℃ for 2 hours, then 0.16g of ammonium bicarbonate and 0.20g of 20wt percent PTFE emulsion are added, ultrasonic treatment is carried out at the temperature of 10 ℃ for 2 hours continuously, third catalyst slurry is obtained, the third cathode catalyst slurry is sprayed on the surface of the second cathode catalyst film far away from the first cathode catalyst film, and the third cathode catalyst film is formed by drying at the temperature of 100 ℃ to obtain the membrane electrode. And the third cathode catalytic film was tested for water contact angle, i.e., porosity, with specific results set forth in table 1.
Steps (5) to (6) are the same as steps (5) to (6) of example 1.
TABLE 1
Note that: f1, F2, F3 represent the first cathode catalytic membrane, the second cathode catalytic membrane, and the third cathode catalytic membrane, respectively.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (14)
1. The preparation method of the membrane electrode is characterized by comprising the following steps:
Providing an anode catalytic layer, a proton exchange membrane and a cathode catalytic membrane group, wherein the cathode catalytic membrane group comprises n layers of cathode catalytic membranes with gradually increased hydrophobicity and porosity, n is an integer not less than 2, and a catalyst in the cathode catalytic membranes is a carbon-supported metal catalyst;
Immersing the n layers of cathode catalytic films in sulfuric acid for corrosion treatment respectively, and as the hydrophobicity and the porosity of the cathode catalytic films are gradually increased, the longer the corrosion treatment is carried out each time and/or the higher the concentration of the sulfuric acid adopted by the corrosion treatment is carried out each time, so as to obtain the n layers of cathode catalytic films after the corrosion treatment:
and arranging the anode catalytic layer on one side of the proton exchange membrane, and arranging the n cathode catalytic membranes subjected to corrosion treatment on the other side of the proton exchange membrane in sequence according to the rule of increasing hydrophobicity and porosity step by step to obtain a membrane electrode.
2. The method of producing a membrane electrode according to claim 1, wherein the minimum concentration of sulfuric acid used for the etching treatment is 10wt%; and/or
The minimum time for the etching treatment was 1h.
3. The method for producing a membrane electrode according to claim 1, wherein the etching treatment is carried out at a temperature of 40 ℃ to 60 ℃.
4. A method of preparing a membrane electrode according to any one of claims 1 to 3 wherein n is 3 and the cathode catalytic membrane group comprises a first cathode catalytic membrane, a second cathode catalytic membrane and a third cathode catalytic membrane having progressively higher hydrophobicity and porosity.
5. The method according to claim 4, wherein the concentrations of the sulfuric acid used in the etching treatment are 10wt% to 20wt%, 20wt% to 30wt%, and 30wt% to 40wt%, respectively, when the etching treatment is performed on the first cathode catalytic film, the second cathode catalytic film, and the third cathode catalytic film, respectively.
6. The method according to claim 4, wherein the etching treatment is performed for 1 to 2 hours, 2 to 3 hours, and 3 to 5 hours on the first cathode catalytic film, the second cathode catalytic film, and the third cathode catalytic film, respectively.
7. The method for producing a membrane electrode according to any one of claim 4, wherein, when the first, second and third cathode catalytic membranes are produced, the mass ratio of the added hydrophobizing agent to the carbon carrier in the catalyst is stepwise increased so that the hydrophobicity of the produced first, second and third cathode catalytic membranes is stepwise increased; and/or
When the first cathode catalytic film, the second cathode catalytic film and the third cathode catalytic film are prepared, the mass ratio of the added pore-forming agent to the carbon carrier in the catalyst is gradually increased, so that the porosities of the prepared first cathode catalytic film, second cathode catalytic film and third cathode catalytic film are gradually increased.
8. The method for producing a membrane electrode according to claim 7, wherein the mass ratio of pore-forming agent to carbon carrier in catalyst used in the production of the first cathode catalyst film is (1-3): (9-7), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (0.5-1.5): (9.5 to 8.5); and/or
When the second cathode catalytic film is prepared, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (3.1-6): (7-4), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (1.5-4.5): (8.5-5.5); and/or
When the third cathode catalytic film is prepared, the mass ratio of the pore-forming agent to the carbon carrier in the catalyst is (6.1-10): (4-1), the mass ratio of the adopted hydrophobizing agent to the carbon carrier in the catalyst is (4.5-5.5): (5.5-4.5).
9. The method for producing a membrane electrode according to any one of claims 7 to 8, wherein the water repellent agent is one or more selected from the group consisting of activated carbon, PTFE emulsion, and polysiloxane.
10. The method for producing a membrane electrode according to any one of claims 7 to 8, wherein the pore-forming agent is one or more selected from the group consisting of ammonium oxalate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, nano PTFE particles, methylcellulose, nano activated carbon, and nano carbon fiber tubes.
11. A method for preparing a cathode catalytic membrane, comprising the steps of:
Mixing a catalyst, an ionomer and a solvent to obtain a catalyst slurry; the catalyst is a carbon-supported metal catalyst;
Coating and drying the catalyst slurry to obtain a catalyst prefabricated film;
And immersing the catalyst prefabricated film in sulfuric acid for corrosion treatment to obtain the cathode catalytic film.
12. The method for preparing a cathode catalytic membrane according to claim 11, wherein the concentration of sulfuric acid is 10wt% to 40wt% for 1h to 6h.
13. A membrane electrode produced by the method for producing a membrane electrode according to any one of claims 1 to 9.
14. A fuel cell comprising the membrane electrode of claim 13.
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