CN114512680A - Preparation method of catalyst layer slurry of proton exchange membrane fuel cell - Google Patents
Preparation method of catalyst layer slurry of proton exchange membrane fuel cell Download PDFInfo
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- CN114512680A CN114512680A CN202210058231.2A CN202210058231A CN114512680A CN 114512680 A CN114512680 A CN 114512680A CN 202210058231 A CN202210058231 A CN 202210058231A CN 114512680 A CN114512680 A CN 114512680A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- 239000002002 slurry Substances 0.000 title claims abstract description 46
- 239000012528 membrane Substances 0.000 title claims abstract description 34
- 239000000446 fuel Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000009736 wetting Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 13
- 239000011949 solid catalyst Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229920000557 Nafion® Polymers 0.000 claims description 9
- 239000000523 sample Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000005457 ice water Substances 0.000 description 11
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000002779 inactivation Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
The invention particularly relates to a preparation method of catalyst layer slurry of a proton exchange membrane fuel cell, belonging to the technical field of fuel cells and comprising the following steps: wetting solid catalyst particles to obtain a wet catalyst; mixing the wet catalyst and the dispersing agent to obtain a mixed solution; mixing and dispersing the mixed solution and the ionic polymer solution to obtain catalyst layer slurry; wherein, the mixing mode of the wetting catalyst and the dispersant is as follows: dropwise adding the wet catalyst to a dispersing agent, wherein the temperature of the dispersing agent is not higher than 10 ℃; by improving the catalyst dispersion mode, the traditional method of adding a dispersing agent into a high-concentration catalyst is changed, and the high-concentration catalyst is slowly dripped into the dispersing agent, so that the concentration and the system temperature of Pt/C in contact with the dispersing agent are reduced as far as possible, the possibility that partial Pt/C which is not completely wetted catalyzes alcohol oxidation reaction to release heat is avoided, and the problem of catalyst agglomeration and deactivation is avoided.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of catalyst layer slurry of a proton exchange membrane fuel cell.
Background
The PEMFC is a latest generation fuel cell, can directly convert chemical energy of hydrogen and oxygen into electric energy as a novel energy processing mode, and has the advantages of low working temperature, no pollution, no corrosion, high specific power, quick start and the like. Proton exchange membrane fuel cells are mainly composed of proton exchange membranes, catalyst layers, carbon paper, bipolar plates and the like, and with the continuous development of fuel cells, more and more high-performance cells are developed, wherein the catalyst layers are the key points influencing the performance of the cells. The catalytic layer is usually composed of supported Pt/C particles, an ionic polymer and a dispersant, and is prepared by processes such as spraying or transfer printing.
In the process of commercial popularization and application of fuel cells, cost is an important reason for restricting the development of the fuel cells. In the manufacturing cost of fuel cells, the cost of the catalyst occupies a large proportion, so that reducing the amount of the noble metal Pt in the catalyst is the main direction of research currently by developers. In the preparation process of the catalyst slurry, in order to ensure the performance and reduce the dosage of the Pt catalyst, high temperature is often avoided, because the temperature rise not only causes the catalyst to agglomerate and reduce the catalytic efficiency, but also causes the catalyst to be oxidized and lose the catalytic activity. Therefore, the temperature is often controlled by means of an ice bath or the like during the dispersion treatment.
The metal Pt is used as transition metal, and can catalyze the oxidation-reduction reaction of hydrogen and oxygen due to the unique outer-layer electronic arrangement, and has good catalytic action on the oxidation reaction of alcohols and alkanes. Isopropanol is a good dispersant and is often used in the dispersion of catalyst slurries. In order to avoid the oxidation and even combustion reaction of isopropanol during the contact of the high-density Pt/C catalyst with isopropanol, the Pt/C catalyst is usually wetted by water, and then the isopropanol is added into the wetted catalyst system for dispersion treatment. However, if the wetting of the Pt/C is insufficient, when the isopropyl alcohol is added, and a small amount of isopropyl alcohol initially contacts the high-concentration catalyst, there is still a possibility that part of the Pt/C which is not fully wetted catalyzes the alcohol oxidation reaction to release heat, and the generated heat cannot be dissipated in the high-concentration catalyst system in time, so that the local temperature of the high-concentration catalyst system is increased, and the catalyst is agglomerated and deactivated; meanwhile, in the process of preparing the wet catalyst, the introduction of more water is also unfavorable for the performance of the membrane electrode.
Therefore, the water content used for wetting the catalyst is reduced, the exothermic oxidation reaction of alcohol caused by insufficient catalyst wetting in the slurry preparation process is avoided, and the control of the system temperature has important significance.
Disclosure of Invention
The method for preparing the catalyst layer slurry of the proton exchange membrane fuel cell aims at solving the problem of catalyst agglomeration and inactivation in the preparation process of the existing catalyst layer slurry to a certain extent, and therefore the method for preparing the catalyst layer slurry of the proton exchange membrane fuel cell is provided.
A first aspect of an embodiment of the present application provides a method for preparing a catalyst layer slurry of a proton exchange membrane fuel cell, where the method includes:
wetting solid catalyst particles to obtain a wet catalyst;
mixing the wet catalyst and a dispersing agent to obtain a mixed solution;
mixing and dispersing the mixed solution and the ionic polymer solution to obtain catalyst layer slurry;
wherein the mixing mode of the wetting catalyst and the dispersant is as follows: the wet catalyst is added dropwise to the dispersant, and the temperature of the dispersant is not higher than 10 ℃.
The method improves the catalyst dispersion mode, changes the traditional method of adding a dispersing agent into a high-concentration catalyst, and slowly drops the high-concentration catalyst into the dispersing agent, thereby reducing the concentration and the system temperature when Pt/C is contacted with the dispersing agent as much as possible, avoiding the possibility that the Pt/C which is not completely wetted catalyzes alcohol oxidation reaction to release heat, and further avoiding the problem of catalyst agglomeration and inactivation.
In addition, the preparation method according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments, the temperature of the dispersant is no greater than 5 ℃.
The lower the temperature of the control dispersant is, the larger the temperature gradient of the contact heating part of the catalytic particles and the dispersant and the ambient environment is, the faster the heat dissipation is, and the agglomeration and deactivation of the catalyst caused by the local temperature rise of the catalytic system can be avoided.
In some embodiments, the drop rate of the wet catalyst is: 1 drop every 1-4 seconds.
The dripping speed of the wet catalyst is controlled, so that sufficient heat dissipation time of contact heating parts of the catalytic particles and the dispersing agent can be provided, catalyst agglomeration and inactivation caused by overhigh local temperature can be effectively avoided, and the catalyst can be dispersed for sufficient time to avoid catalyst agglomeration.
In some embodiments, the dropwise addition is accompanied by agitation at a rate of at least 400 rpm.
The catalyst particles can be rapidly dispersed to generate heat when being contacted with the dispersing agent by adding the stirring, and simultaneously, the catalyst particles can be rapidly dispersed to avoid agglomeration, thereby avoiding the agglomeration and inactivation of the catalyst.
In some embodiments, the mass fraction of Pt/C in the solid catalyst particles is between 40% and 70%.
The specific surface area of the metal platinum in the system can be increased, the catalytic performance is improved, and the using amount of the metal platinum is reduced by controlling the mass ratio of Pt/C to be 40-70%, wherein if the mass ratio is too large, the platinum atoms are easy to agglomerate, and if the mass ratio is too small, the platinum content is too low to achieve the ideal catalytic performance.
In some embodiments, the dispersant comprises isopropyl alcohol.
In some embodiments, the composition of the ionic polymer comprises, by mass: nafion solution 4% -6%, isopropanol 48% -50% and water 46% -48%.
The ionic polymer in the nafion solution can be better dissolved by controlling the proportion of the components, and the dispersion of the ionic polymer in the slurry is facilitated.
In some embodiments, the catalytic layer slurry has a water-alcohol mass ratio of 1: 9-1: 18.
controlling the water-alcohol mass ratio of the catalyst layer slurry to be 1: 9-1: 18, the catalyst is prevented from being wetted as much as possible, the performance of the catalyst layer is reduced due to the fact that more water is introduced into the slurry, and the catalyst is prevented from being wetted seriously to cause heat release and agglomeration of the catalyst in the slurry preparation process due to the fact that the ratio is too small.
In some embodiments, the catalytic layer slurry has a mass ratio of ionomer to carbon support of 0.5 to 1: 1.
controlling the mass ratio of the ionic polymer to the carbon carrier to be 0.5-1: 1, the ionic polymer is used as a bonding agent, so that the dispersion of the platinum-carbon catalyst in a system is facilitated, the proton conductivity of the catalyst layer is increased, the mass transfer resistance of the catalyst layer is increased and platinum atoms are possibly wrapped when the mass ratio is too large, and a good bonding effect cannot be achieved when the mass ratio is too small.
In some embodiments, the dispersing comprises at least one of stirring, water bath ultrasound, and probe ultrasound, and the dispersing time is 0.5h to 3 h.
In some embodiments, the wetting of the solid catalyst particles to obtain a wetted catalyst specifically comprises:
the solid catalyst particles and water were mixed with a shear to obtain a wet catalyst.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method provided by an embodiment of the present invention;
fig. 2 is a graph showing the results of electrochemical properties of catalyst pastes provided in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the examples of the present application will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings 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. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
the applicant finds in the course of the invention that: in order to avoid the oxidation and even combustion reaction of isopropanol in the process of contacting the high-density Pt/C catalyst with the isopropanol, the Pt/C catalyst is wetted by water, and then the isopropanol is added into a wetted catalyst system for dispersion treatment; however, if the wetting of the Pt/C is not sufficient, when the isopropanol is added, and a small amount of isopropanol initially contacts the high-concentration catalyst, there is still a possibility that part of the incompletely wetted Pt/C catalyzes the alcohol oxidation reaction to release heat, and the generated heat cannot be dissipated in the high-concentration catalyst system in time, so that the local temperature of the high-concentration catalyst system is increased, and the catalyst is agglomerated and deactivated; meanwhile, in the process of wetting the catalyst, the introduction of more water is also unfavorable for the performance of the membrane electrode.
The application aims to provide a preparation method of catalyst layer slurry of a proton exchange membrane fuel cell with better performance, so as to achieve the purpose of avoiding catalyst agglomeration and inactivation on the premise of not influencing the performance of a membrane electrode.
The embodiment provides a preparation method of catalyst layer slurry of a proton exchange membrane fuel cell, which comprises the following steps:
s1, wetting solid catalyst particles to obtain a wet catalyst;
specifically, solid catalyst particles and deionized water are mixed and wetted by a shearing machine to obtain a wet catalyst;
in some embodiments, the mass ratio of Pt/C in the solid catalyst particles is from 40% to 70%, including but not limited to 40%, 45%, 50%, 55%, 60%, 65%, and 70%.
S2, mixing the wet catalyst and a dispersing agent to obtain a mixed solution;
in some embodiments, the wet catalyst and the dispersant are mixed by: the wet catalyst is added dropwise to the dispersant at a temperature of no more than 10 ℃, including but not limited to 10 ℃, 9 ℃, 8 ℃, 7 ℃, 6 ℃, 5 ℃, 4 ℃, 3 ℃, 2 ℃, 1 ℃ and 0 ℃.
In some embodiments, the temperature of the dispersant is no greater than 5 ℃.
In practical operation, the dispersant is usually placed in an ice bath, and isopropanol is used as a good dispersant and is mostly used for dispersing the catalyst slurry, so that isopropanol is selected as the dispersant in the embodiment.
In some embodiments, the drop rate of the wet catalyst is: 1 drop every 1-4 seconds, drop rates include, but are not limited to, 1 drop every 1 second, 1 drop every 2 seconds, 1 drop every 3 seconds, and 1 drop every 4 seconds.
In some embodiments, the dropwise addition is accompanied by agitation at a rate of at least 400 rpm, including, but not limited to, 400 rpm, 450 rpm, 500 rpm, 550 rpm, and 600 rpm.
S3, mixing and dispersing the mixed solution and the ionic polymer solution to obtain catalyst layer slurry;
in some embodiments, the composition of the ionic polymer comprises, by mass: nafion solution 4% -6%, nafion solution mass ratio including but not limited to 4%, 4.5%, 5%, 5.5% and 6%, isopropanol 48% -50%, isopropanol mass ratio including but not limited to 48%, 48.5%, 49%, 49.5% and 50%, water 46% -48%, water mass ratio including but not limited to 46%, 46.5%, 47%, 47.5% and 48%.
In specific implementation, the dispersing manner can be at least one selected from stirring, water bath ultrasound and probe ultrasound, the dispersing time is 0.5h-3h, and the dispersing time includes but is not limited to 0.5h, 1h, 1.5h, 2h, 2.5h and 3 h.
The preparation method of the catalyst layer slurry of the proton exchange membrane fuel cell of the present application will be described in detail below with reference to examples, comparative examples and experimental data.
Example 1
A preparation method of catalyst layer slurry of a proton exchange membrane fuel cell comprises the following steps:
(1) TKK 47% Pt/C1.03 g was weighed out, added to 3.20g water and mixed for 2 minutes at 2800 rpm with a shear
(2) The wetted catalyst from step 1) was added dropwise at a rate of one drop per second to 56g of low temperature (ice-water bath) isopropanol stirred at 500 revolutions per second
(3) To the mixture obtained in step 2) was added 7.35g of a Nafion (5.2%) solution from DuPont. Mechanically stirring for 3 hours at room temperature, carrying out ultrasonic treatment in an ice-water bath for half an hour, and carrying out ultrasonic treatment on a probe in the ice-water bath for half an hour. Thus obtaining the catalyst slurry which takes isopropanol as a dispersant and has I/C ratio of 0.7:1 and water-alcohol ratio of 1: 9.
Example 2
A preparation method of catalyst layer slurry of a proton exchange membrane fuel cell comprises the following steps:
(1) weighing 1.03g of TKK 47% Pt/C, adding into 1.3g of water, mixing at 2800 rpm for 2 minutes by a shearing machine, and stirring for 2 minutes;
(2) the wetted catalyst from step 1) was added dropwise at a rate of two seconds one drop to 58g of isopropanol stirred at 500 revolutions per second in a low-temperature (ice-water bath) bath;
(3) to the mixture obtained in step 2) was added 4.3g of a solution of Nafion (5.2%) from DuPont. Mechanically stirring for 3 hours at room temperature, carrying out ultrasonic treatment in an ice-water bath for half an hour, and carrying out ultrasonic treatment on a probe in the ice-water bath for half an hour. Thus obtaining the catalyst slurry which takes isopropanol as a dispersant and has I/C ratio of 0.7:1 and water-alcohol ratio of 1: 13.
Example 3
A preparation method of catalyst layer slurry of a proton exchange membrane fuel cell comprises the following steps:
(1) weighing 0.81g of Jiping 60% Pt/C, adding into 0.5g of water, and mixing for 2 minutes at 2800 rpm by a shearing machine;
(2) the wetted catalyst from step 1) was added dropwise at a rate of one drop per second to 43g of low temperature (ice-water bath) isopropanol stirred at 500 revolutions per second;
(3) to the mixture obtained in step 2) was added 4.3g of a solution of Nafion (5.2%) from DuPont. Mechanically stirring for 3 hours at room temperature, carrying out ultrasonic treatment in an ice-water bath for half an hour, and carrying out ultrasonic treatment on a probe in the ice-water bath for half an hour. Thus obtaining the catalyst slurry which takes isopropanol as a dispersant and has I/C ratio of 0.7:1 and water-alcohol ratio of 1: 18.
Comparative example 1
A preparation method of catalyst layer slurry of a proton exchange membrane fuel cell comprises the following steps:
(1) weighing 1.03g of TKK 47% Pt/C, adding into 1.3g of water, and mixing for 2 minutes at 2800 rpm with a shearing machine;
(2) to the wetted catalyst obtained in step 1, 7.35g of a Nafion (5.2%) solution from DuPont and 55g of isopropanol were added. Mechanically stirring for 3 hours at room temperature, carrying out ultrasonic treatment in an ice-water bath for half an hour, and carrying out ultrasonic treatment on a probe in the ice-water bath for half an hour. Thus obtaining the catalyst slurry which takes isopropanol as a dispersant and has I/C ratio of 0.7:1 and water-alcohol ratio of 1: 13.
Examples of the experiments
The proton exchange membrane fuel cell catalyst slurry of examples 1-3 and comparative example 1 were prepared to 25cm for each example2The electrochemical properties of the membrane electrode were measured by a polarization curve, and the results are shown in FIG. 1, from which it can be seen that the membrane electrode prepared from the catalyst pastes of examples 1 to 3 had the propertiesBetter than comparative example 1, especially at high current densities, as shown in FIG. 1, example 3 at 2200mA/cm2The voltage is 0.57V at the current density of (1); in contrast, in comparative example 1, the voltage was only 0.47V at the same current density.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) according to the method provided by the embodiment of the invention, the traditional dispersion mode is changed, and a mode of slowly dripping the high-concentration wet catalyst into the stirred low-temperature dispersing agent is adopted, so that the local oxidation exothermic reaction caused by the partial non-wet catalyst when a small amount of isopropanol is contacted with the high-concentration catalyst is avoided;
(2) the method provided by the embodiment of the invention reduces the water consumption required by wetting the catalyst, and avoids the performance reduction of the membrane electrode caused by more water content of the system;
(3) the method provided by the embodiment of the invention greatly reduces the concentration of the catalyst when contacting isopropanol, and reduces the possibility of isopropanol oxidation exothermic reaction caused by insufficient catalyst wetting;
(4) the method provided by the embodiment of the invention can timely dissipate heat generated by isopropanol oxidation exothermic reaction caused by insufficient catalyst wetting in a large amount of low-temperature isopropanol systems, avoid the possibility of local temperature rise, further avoid the problems of catalyst agglomeration and oxidation inactivation caused by temperature rise, and further improve the electrochemical performance of the membrane electrode.
Finally, it should also be 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 application have been described, additional variations and modifications of these embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including 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 in the present invention without departing from the spirit or scope of the embodiments of the application. Thus, if such modifications and variations of the embodiments of the present application fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of catalyst layer slurry of a proton exchange membrane fuel cell is characterized by comprising the following steps:
wetting solid catalyst particles to obtain a wet catalyst;
mixing the wet catalyst and a dispersing agent to obtain a mixed solution;
mixing and dispersing the mixed solution and the ionic polymer solution to obtain catalyst layer slurry;
wherein the mixing mode of the wetting catalyst and the dispersant is as follows: the wet catalyst is added dropwise to the dispersant, and the temperature of the dispersant is not higher than 10 ℃.
2. The preparation method of the catalyst layer slurry for the proton exchange membrane fuel cell according to claim 1, wherein the temperature of the dispersant is not higher than 5 ℃.
3. The method for preparing the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 1, wherein the dropping speed of the wet catalyst is as follows: 1 drop every 1-4 seconds.
4. The method for preparing the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 1, wherein the dropping is accompanied by stirring, and the stirring speed is at least 400 rpm.
5. The preparation method of the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 1, wherein the mass ratio of Pt/C in the solid catalyst particles is 40-70%.
6. The method of preparing a catalyst layer slurry for a proton exchange membrane fuel cell according to claim 1, wherein the dispersant comprises isopropyl alcohol.
7. The method for preparing the catalytic layer slurry of the proton exchange membrane fuel cell according to claim 6, wherein the ionic polymer comprises the following components by mass: nafion solution 4% -6%, isopropanol 48% -50% and water 46% -48%.
8. The preparation method of the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 6, wherein the catalyst layer slurry has a water-alcohol mass ratio of 1: 9-1: 18.
9. the preparation method of the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 1, wherein the mass ratio of the ionic polymer to the carbon carrier in the catalyst layer slurry is 0.5-1: 1.
10. the preparation method of the catalyst layer slurry of the proton exchange membrane fuel cell according to claim 1, wherein the dispersing manner comprises at least one of stirring, water bath ultrasound and probe ultrasound, and the dispersing time is 0.5h-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210058231.2A CN114512680B (en) | 2022-01-19 | 2022-01-19 | Preparation method of proton exchange membrane fuel cell catalytic layer slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210058231.2A CN114512680B (en) | 2022-01-19 | 2022-01-19 | Preparation method of proton exchange membrane fuel cell catalytic layer slurry |
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| Publication Number | Publication Date |
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| CN114512680A true CN114512680A (en) | 2022-05-17 |
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