CN111370717A - Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell - Google Patents
Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 216
- 239000002002 slurry Substances 0.000 title claims abstract description 97
- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 239000000446 fuel Substances 0.000 title claims abstract description 27
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 51
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000006229 carbon black Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 28
- 229920000831 ionic polymer Polymers 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000009792 diffusion process Methods 0.000 claims description 11
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
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- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
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- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 20
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- 229910002837 PtCo Inorganic materials 0.000 description 8
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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
- H01M4/90—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- 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 relates to cathode catalyst slurry, a cathode catalyst layer, a membrane electrode and a fuel cell, and relates to the technical field of fuel cells. The main technical scheme adopted is as follows: a cathode catalyst slurry for preparing a cathode catalyst layer of a fuel cell, wherein the cathode catalyst slurry comprises: catalyst slurry body and hydrophobic white carbon black; wherein the catalyst slurry body contains a carbon-supported noble metal catalyst; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier; the mass of the hydrophobic white carbon black is 0.1-8% of the mass of the carbon carrier. The invention is mainly used for discharging water generated in the cathode catalyst layer of the membrane electrode easily and ensuring the catalytic performance of the membrane electrode.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to cathode catalyst slurry, a cathode catalyst layer, a membrane electrode and a fuel cell.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are clean energy sources that directly convert chemical energy into electrical energy. The method has the advantages of high conversion efficiency, high power density, low-temperature operation, no pollution and the like, and has wide application prospect in the fields of power automobiles, medium and small power stations, mobile electronic equipment and the like.
The Membrane Electrode (MEA) is the core component of the proton exchange membrane and consists of an anode gas diffusion layer, an anode catalyst layer, the proton exchange membrane, a cathode catalyst layer and a cathode gas diffusion layer. The performance of the membrane electrode directly determines the performance of the fuel cell, and the preparation of the high-performance and high-power membrane electrode has great significance for the commercialization of the fuel cell. The catalyst layer of the membrane electrode is a place where chemical reaction occurs, and generally consists of a noble metal catalyst (such as Pt/C) and an ionic polymer (such as Nafion), wherein the carbon-supported catalyst particles realize electron conduction, and the ionic polymer is responsible for proton conduction, and the two together form a complex network porous structure capable of conducting reaction gas and water.
Water is generated by reaction in a cathode catalyst layer of the membrane electrode, if the generated water is not discharged in time, a flooding phenomenon is generated, the activity of the catalyst is reduced, and the diffusion of cathode reaction gas is hindered, and particularly under the condition of high current density, the performance of the membrane electrode is greatly reduced. Cathode water management of membrane electrodes has also been the focus of recent research to improve cathode water management in an efficient manner, prevent flooding, and improve membrane electrode performance.
In order to avoid the flooding phenomenon mentioned above, in the prior art, polytetrafluoroethylene is incorporated to adjust the wetting angle of the membrane electrode with respect to water when preparing the cathode catalyst layer of the membrane electrode. However, the inventors of the present invention found that: the polytetrafluoroethylene is also a binder and is easy to cover the surface of the carbon-supported noble metal catalyst, so that the utilization rate of noble metal is reduced, and the cathode catalytic performance of the membrane electrode is influenced.
Disclosure of Invention
In view of the above, the present invention provides a cathode catalyst slurry, a cathode catalyst layer, a membrane electrode, and a fuel cell, and aims to easily discharge water generated by a reaction in a cathode catalyst layer of the membrane electrode and to ensure catalytic performance of the membrane electrode.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide a cathode catalyst slurry for preparing a cathode catalyst layer of a fuel cell, wherein the cathode catalyst slurry includes:
a catalyst slurry body containing a carbon-supported noble metal catalyst; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier;
the mass of the hydrophobic white carbon black is 0.1-8% of that of the carbon carrier.
Preferably, the carbon support is any one of conductive carbon black, carbon nanotubes, and carbon nanofibers.
Preferably, in the carbon-supported noble metal catalyst, the content of the noble metal is 10 to 80%.
Preferably, the noble metal is one or more of Pt, Pd, Ru and Ir; or the noble metal comprises a noble metal body and a doped metal; wherein the noble metal body comprises one or more of Pt, Pd, Ru and Ir; the doped metal comprises one or more of Fe, Co, Ni and Cr.
Preferably, the catalyst slurry body also contains an ionic polymer; wherein the mass ratio of the ionic polymer to the carbon support is 0.5 to 2.0. Preferably, the ionic polymer is perfluorosulfonic acid resin.
Preferably, the catalyst slurry body also contains a solvent; wherein the solid content of the cathode catalyst slurry is 0.5-40 wt%; preferably, the solvent is an alcoholic solvent, preferably isopropanol.
On the other hand, the preparation method of the cathode catalyst slurry comprises the following steps:
mixing the raw material of the catalyst slurry body and hydrophobic white carbon black, and performing dispersion treatment to obtain catalyst slurry;
preferably, the solvent, the ionic polymer or ionic polymer solution, the carbon-supported noble metal catalyst and the hydrophobic white carbon black are mixed and then dispersed to obtain the cathode catalyst slurry.
Preferably, the dispersion treatment is one or more of ultrasonic treatment, ball milling treatment and mechanical shearing treatment.
On the other hand, the embodiment of the invention also provides a cathode catalyst layer, wherein the cathode catalyst layer contains a carbon-supported noble metal catalyst and hydrophobic white carbon black; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier; the mass of the hydrophobic white carbon black is 0.1-8% of the mass of the carbon carrier.
Preferably, the cathode catalyst layer further contains an ionic polymer; further preferably, the mass ratio of the ionic compound to the carbon support is 0.5 to 2.0; further preferably, the ionic polymer is perfluorosulfonic acid resin;
preferably, the cathode catalyst layer is obtained by coating any one of the cathode catalyst slurries on a proton exchange membrane and drying the cathode catalyst slurry; further preferably, the coating mode is ultrasonic spraying.
In still another aspect, an embodiment of the present invention provides a membrane electrode, wherein the membrane electrode includes the above-mentioned cathode catalyst layer.
In another aspect, the method for preparing the membrane electrode comprises the following steps:
coating the cathode catalyst slurry on one side of a proton exchange membrane to form a cathode catalyst layer, and coating the anode catalyst slurry on the other side of the proton exchange membrane to form an anode catalyst layer, thereby obtaining CCM (CCM refers to a catalyst/proton exchange membrane assembly prepared by coating fuel cell catalysts on two sides of the proton exchange membrane, and is called CCM (catalyst coated membrane) for short;
arranging gas diffusion layers on two sides of the CCM to obtain a membrane electrode;
preferably, the coating mode is ultrasonic spraying.
In still another aspect, an embodiment of the present invention provides a fuel cell, wherein the fuel cell includes the membrane electrode described above.
Compared with the prior art, the cathode catalyst slurry, the cathode catalyst layer, the membrane electrode and the fuel cell have the following beneficial effects:
according to the cathode catalyst slurry, the cathode catalyst layer, the membrane electrode and the fuel cell provided by the embodiment of the invention, the hydrophobic white carbon black is added into the catalyst slurry body, so that water generated in the cathode catalyst layer of the membrane electrode by reaction is easy to discharge, the diffusion capacity of reaction gas in the cathode catalyst layer is improved, and the performance of the cathode catalyst layer of the membrane electrode of the fuel cell is improved. The content of the hydrophobic white carbon black is controlled to be 0.1-8% of the mass of the carbon carrier in the carbon-supported noble metal catalyst, so that the hydrophobic effect of the cathode catalyst slurry is ensured, and the conductivity of a cathode catalyst layer of the membrane electrode is also ensured.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a graph comparing the polarization curves of single cells of the membrane electrodes prepared in examples 1, 2 and 3 of the present invention with those of the blank membrane electrodes prepared in comparative examples 1 and 2 under the conditions of 70 ℃ of hydrogen-air cell temperature, 30psi of cathode-anode back pressure and 100% of relative humidity;
FIG. 2 is a graph comparing the polarization curves of single cells of the membrane electrodes prepared in examples 4, 5 and 6 of the present invention with those of the blank membrane electrodes prepared in comparative examples 3 and 4 under the conditions of 70 ℃ of hydrogen-air cell temperature, 30psi of cathode-anode back pressure and 100% of relative humidity.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, an embodiment of the present invention provides a cathode catalyst slurry for preparing a cathode catalyst layer of a fuel cell, where the cathode catalyst slurry includes a catalyst slurry bulk and hydrophobic white carbon black. The catalyst slurry body consists of a carbon-supported noble metal catalyst, an ionic polymer and a solvent; or the catalyst slurry body consists of the carbon-supported noble metal catalyst, the ionic polymer solution and the solvent. Wherein, the mass of the hydrophobic white carbon black is 0.1-8% of the mass of the carbon carrier in the carbon-supported noble metal catalyst.
In the cathode catalyst slurry provided by the embodiment of the invention, the hydrophobic white carbon black is added into the catalyst slurry body, so that water generated in the reaction in the cathode catalyst layer of the membrane electrode is easy to discharge, and the reaction gas diffusion capability of the cathode catalyst layer is further improved, thereby improving the performance of the cathode catalyst layer of the membrane electrode of the fuel cell. And the content of the hydrophobic white carbon black is 0.1-8% of the mass of the carbon carrier in the catalyst. In the cathode catalyst slurry, if the mass of the hydrophobic white carbon black is less than 0.1% of the mass of the carbon carrier, the hydrophobic effect is not obvious; if the mass of the hydrophobic white carbon black is higher than 8% of the mass of the carbon carrier, the internal resistance of the catalyst layer becomes very obvious due to poor electrical conductivity of the hydrophobic white carbon black.
Preferably, the carbon support is any one of conductive carbon black, carbon nanotubes, and carbon nanofibers.
Preferably, in the carbon-supported noble metal catalyst, the content of the noble metal is 10 to 80 percent.
Preferably, the noble metal is one or more of Pt, Pd, Ru and Ir; or the noble metal comprises a noble metal body and a doped metal; wherein the noble metal body comprises one or more of Pt, Pd, Ru and Ir; the doped metal comprises one or more of Fe, Co, Ni and Cr. That is, the noble metal includes, but is not limited to, noble metals such as Pt, Pd, Ru, Ir, etc., binary alloys of PtPd, PtRu, PtIr noble metals, and binary alloys and ternary alloys with Fe, Co, Ni, Cr.
Preferably, the ionic polymer refers to perfluorosulfonic acid resin containing sulfonic acid groups and having proton exchange capacity; for example, when preparing a cathode catalyst slurry, Nafion resin or solution from Chemours, or Aquivion solution from Solvay is used.
Preferably, the catalyst slurry body also contains a solvent; wherein the solid content of the cathode catalyst slurry is 0.5-40 wt%; the solvent is an alcohol solvent, preferably isopropanol.
Here, the method for preparing the cathode catalyst slurry includes the steps of: after ionic polymer is added into a solvent and uniformly dispersed, carbon-supported noble metal catalyst and hydrophobic white carbon black are added, and after any one of ultrasonic (ultrasonic), ball milling and mechanical shearing (homogenizer) dispersion treatment, uniform dispersion is obtained to obtain catalyst slurry. And spraying or coating the slurry on a proton exchange membrane, and drying to obtain the membrane electrode catalyst layer.
On the other hand, the embodiment of the invention also provides a cathode catalyst layer, wherein the cathode catalyst layer contains a carbon-supported noble metal catalyst, an ionic polymer and hydrophobic white carbon black; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier; the mass of the hydrophobic white carbon black is 0.1-8% of the mass of the carbon carrier. Wherein the cathode catalyst layer is formed by coating the cathode catalyst slurry on a proton exchange membrane(preferably, the loading amount of the noble metal in the cathode catalyst layer is 0.05-0.8mg/cm2) And drying to obtain the product.
In another aspect, an embodiment of the present invention provides a membrane electrode, where the membrane electrode includes the above-mentioned cathode catalyst layer. Preferably, the membrane electrode comprises a CCM and gas diffusion layers positioned on two sides of the CCM; wherein the CCM includes: a proton exchange membrane, an anode catalyst layer and a cathode catalyst layer; wherein the anode catalyst layer is coated on one side of the proton exchange membrane, and the cathode catalyst layer is coated on the other side of the proton exchange membrane
The preparation method of the membrane electrode comprises the following steps:
1) coating the cathode catalyst slurry on one side of the proton exchange membrane to form a cathode catalyst layer, and coating the anode catalyst slurry on the other side of the proton exchange membrane to form an anode catalyst layer, thereby obtaining CCM (CCM refers to a catalyst/proton exchange membrane assembly prepared by coating fuel cell catalysts on two sides of the proton exchange membrane, and is called CCM (purified coated membrane) for short).
2) Arranging gas diffusion layers on two sides of the CCM to obtain a membrane electrode; preferably, the coating treatment is ultrasonic spraying.
In still another aspect, an embodiment of the present invention provides a fuel cell, wherein the fuel cell includes the membrane electrode described above.
The invention is further illustrated by the following specific examples:
example 1
Preparing cathode catalyst slurry: mixing a Pt/C catalyst with the Pt content of 70%, hydrophobic white carbon black, a perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent, and dispersing the mixture into cathode catalyst slurry by ultrasonic waves. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 0.1 percent of the mass of the carbon carrier in the Pt/C catalyst, the I/C ratio is 1:1(I/C is the mass ratio of the ionic polymer to the carbon carrier), and the solid content is 2 weight percent.
Preparing anode catalyst slurry: a Pt/C catalyst with 70% Pt content, a perfluorosulfonic acid ionomer solution (5 wt% Nafion, Chemours) and isopropanol as a solvent were mixed and dispersed by ultrasonic waves to form an anode catalyst slurry. Wherein, in the anode catalyst slurry: the I/C ratio was 1:1 and the solids content was 2% by weight.
Preparing a membrane electrode: in order to test the performance of the catalytic layer, the loading amount of Pt in the anode catalytic layer is 0.1mg/cm2The loading capacity of the cathode catalyst layer Pt is 0.4mg/cm2Ultrasonic spraying is respectively carried out on two sides of a Nafion211 proton exchange membrane to form CCM, the area of an active area is 5cm × 5cm, and then gas diffusion layers (SGL company) with the length of 5cm × 5cm are attached to the two sides of the CCM to obtain the membrane electrode.
Activation and performance test: the membrane electrode is placed in a single cell, activated for 2 hours under the conditions that the temperature of the cell is 70 ℃ and the cathode and the anode are completely humidified, and repeatedly discharged to be fully activated. The battery performance test conditions were as follows: the fuel gas is hydrogen, the oxidant is air, the temperature of the cell is 70 ℃, the back pressure of the cathode and the anode is 30psi, and the relative humidity of the cathode and the anode is 100%.
Example 2
Example 2 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in example 2 was prepared as follows:
mixing a Pt/C catalyst with 70 percent of Pt content, hydrophobic white carbon black, a perfluorinated sulfonic acid ionic polymer solution (5 weight percent of Nafion, Chemours company) and isopropanol serving as a solvent, and performing ball milling to disperse the mixture into cathode catalyst slurry. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 3% of the mass of the carbon carrier in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
Example 3
Example 3 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The preparation procedure of the cathode catalyst slurry in example 3 was as follows:
Pt/C catalyst with 70% Pt content, hydrophobic white carbon black, perfluorinated sulfonic acid ionic polymer solution (25 wt% PFSA, Solvay company) and isopropanol solvent are mixed and dispersed into cathode catalyst slurry by a homogenizer. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 8% of the mass of the carbon carrier in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
Example 4
Example 4 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in example 4 was prepared as follows:
a PtCo/C catalyst with the Pt content of 46.4% and the Co content of 5% by mass, hydrophobic white carbon black, a perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent are mixed and then dispersed into cathode catalyst slurry through ultrasonic waves. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 0.2 percent of the mass of the carbon carrier in the PtCo/C catalyst, the I/C ratio is 1:1, and the solid content is 2 weight percent.
Example 5
Example 5 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in example 5 was prepared as follows:
a PtCo/C catalyst with the Pt content of 46.4 percent and the Co content of 5 percent by mass, hydrophobic white carbon black, perfluorinated sulfonic acid ionic polymer solution (5 percent by weight of Nafion, Chemours company) and isopropanol serving as a solvent are mixed and dispersed into cathode catalyst slurry through ball milling. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 4 percent of the weight of the carbon carrier in the PtCo/C catalyst, the I/C ratio is 1:1, and the solid content is 2 weight percent.
Example 6
Example 6 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in example 6 was prepared as follows:
a PtCo/C catalyst with a Pt content of 46.4% by mass and a Co content of 5% by mass, hydrophobic white carbon black, a perfluorosulfonic acid ionomer solution (25 wt% PFSA, Solvay Co.) and isopropanol as a solvent were mixed and dispersed into cathode catalyst slurry by a homogenizer. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 7 percent of the weight of the carbon carrier in the PtCo/C catalyst, the I/C ratio is 1:1, and the solid content is 2 weight percent.
Comparative example 1
Comparative example 1 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The preparation procedure of the cathode catalyst slurry in comparative example 1 was as follows:
a Pt/C catalyst with 70% Pt content, a perfluorosulfonic acid ionomer solution (5 wt% Nafion, Chemours) and isopropanol as a solvent were mixed and dispersed by ultrasonic waves to obtain a cathode catalyst slurry. Wherein, in the cathode catalyst slurry: the I/C ratio was 1:1 and the solids content was 2% by weight.
Comparative example 2
Comparative example 2 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in comparative example 2 was prepared as follows:
Pt/C catalyst with 70 percent of Pt content, hydrophobic white carbon black, perfluorinated sulfonic acid ionic polymer solution (5 weight percent of Nafion, Chemours company) and isopropanol solvent are mixed and dispersed into cathode catalyst slurry by ultrasonic wave. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 10% of the mass of the carbon carrier in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
Comparative example 3
Comparative example 3 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The preparation procedure of the cathode catalyst slurry in comparative example 3 was as follows:
mixing a PtCo/C catalyst with the Pt content of 46.4 percent by mass and the Co content of 5 percent by mass, a perfluorinated sulfonic acid ionomer solution (25wt percent PFSA, Solvay company) and isopropanol serving as a solvent, and dispersing the mixture into cathode catalyst slurry by using a homogenizer; wherein, in the cathode catalyst slurry: the I/C ratio was 1:1 and the solids content was 2% by weight.
Comparative example 4
Comparative example 4 differs from example 1 in that: the preparation steps of the cathode catalyst slurry are different, and the rest steps are completely consistent. The cathode catalyst slurry in comparative example 4 was prepared as follows:
a PtCo/C catalyst with a Pt content of 46.4% by mass and a Co content of 5% by mass, hydrophobic white carbon black, a perfluorosulfonic acid ionomer solution (25 wt% PFSA, Solvay Co.) and isopropanol as a solvent were mixed and dispersed into cathode catalyst slurry by a homogenizer. Wherein, in the cathode catalyst slurry: the hydrophobic white carbon black accounts for 0.05 wt% of the weight of the carbon carrier in the catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
FIG. 1 is a graph comparing the polarization curves of unit cells of the membrane electrodes prepared in examples 1, 2 and 3 with those of the blank membrane electrodes prepared in comparative examples 1 and 2 at a hydrogen-air cell temperature of 70 ℃, a cathode-anode back pressure of 30psi and a relative humidity of 100%. As is apparent from fig. 1, the cathode catalyst layer without hydrophobic white carbon black is difficult to discharge due to too much water generated under high current density, and the output voltage is sharply reduced due to "flooding" (see the polarization curve of comparative example 1). After the hydrophobic white carbon black is added, the output voltage drops slowly under the condition of large current density (see polarization curves of example 1-example 3); however, the hydrophobic white carbon black is added too much, and the output voltage is reduced greatly due to the larger resistance (see the polarization curve of comparative example 2).
FIG. 2 is a graph comparing the polarization curves of single cells of the membrane electrodes prepared in examples 4, 5 and 6 of the present invention with those of the blank membrane electrodes prepared in comparative examples 3 and 4 under the conditions of 70 ℃ of hydrogen-air cell temperature, 30psi of cathode-anode back pressure and 100% of relative humidity. As is apparent from fig. 2, the cathode catalyst layer without hydrophobic white carbon black is difficult to discharge due to too much moisture generated under a high current density, "flooding" causes a sharp drop in output voltage (see the polarization curve of comparative example 3). After the hydrophobic white carbon black is added, the output voltage drops slowly under the condition of high current density (see the polarization curves of examples 4-6); however, the hydrophobic white carbon black is added too little, and the performance improvement is not obvious (see the polarization curve of comparative example 4).
In summary, according to the cathode catalyst slurry, the cathode catalyst layer, the membrane electrode and the fuel cell provided by the embodiment of the invention, the hydrophobic white carbon black is added into the catalyst slurry body, so that water generated by reaction in the cathode catalyst layer of the membrane electrode is easy to discharge, the diffusion capability of reaction gas in the cathode catalyst layer is improved, and the performance of the cathode catalyst layer of the membrane electrode of the fuel cell is improved. The content of the hydrophobic white carbon black is controlled to be 0.1-8% of the mass of the carbon carrier in the carbon-supported noble metal catalyst, so that the hydrophobic effect of the cathode catalyst slurry is ensured, and the conductivity of a cathode catalyst layer of the membrane electrode is also ensured.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. A cathode catalyst slurry for preparing a cathode catalyst layer of a fuel cell, the cathode catalyst slurry comprising:
a catalyst slurry body containing a carbon-supported noble metal catalyst; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier;
the mass of the hydrophobic white carbon black is 0.1-8% of that of the carbon carrier.
2. The cathode catalyst ink according to claim 1,
the carbon carrier is any one of conductive carbon black, carbon nano tubes and carbon nano fibers; and/or
In the carbon-supported noble metal catalyst, the content of the noble metal is 10 to 80%.
3. The cathode catalyst ink according to claim 1,
the noble metal is one or more of Pt, Pd, Ru and Ir; or
The noble metal comprises a noble metal body and a doped metal; wherein the noble metal body comprises one or more of Pt, Pd, Ru and Ir; the doped metal comprises one or more of Fe, Co, Ni and Cr.
4. The cathode catalyst ink according to any one of claims 1 to 3, wherein the catalyst ink bulk further contains an ionic polymer; wherein the mass ratio of the ionic polymer to the carbon support is 0.5 to 2.0;
preferably, the ionic polymer is perfluorosulfonic acid resin.
5. The cathode catalyst ink according to any one of claims 1 to 3, wherein the catalyst ink bulk further contains a solvent; wherein,
the solid content of the cathode catalyst slurry is 0.5-40 wt%;
preferably, the solvent is an alcoholic solvent, preferably isopropanol.
6. The method for preparing the cathode catalyst ink according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing the raw material of the catalyst slurry body and hydrophobic white carbon black, and performing dispersion treatment to obtain catalyst slurry;
preferably, after mixing the solvent, the ionic polymer or ionic polymer solution, the carbon-supported noble metal catalyst and the hydrophobic white carbon black, performing dispersion treatment to obtain cathode catalyst slurry;
preferably, the dispersion treatment is one or more of ultrasonic treatment, ball milling treatment and mechanical shearing treatment.
7. The cathode catalyst layer is characterized by comprising a carbon-supported noble metal catalyst and hydrophobic white carbon black; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier; the mass of the hydrophobic white carbon black is 0.1-8% of that of the carbon carrier;
preferably, the cathode catalyst layer further contains an ionic polymer; further preferably, the mass ratio of the ionic compound to the carbon support is 0.5 to 2.0; further preferably, the ionic polymer is perfluorosulfonic acid resin;
preferably, the cathode catalyst layer is obtained by coating the cathode catalyst slurry according to any one of claims 1 to 6 on a proton exchange membrane and drying the coating.
8. A membrane electrode, wherein the membrane electrode comprises the cathode catalyst layer of claim 7.
9. The method for preparing a membrane electrode according to claim 8, comprising the steps of:
applying the cathode catalyst ink of any one of claims 1 to 6 to one side of a proton exchange membrane to form a cathode catalyst layer and applying the anode catalyst ink to the other side of the proton exchange membrane to form an anode catalyst layer to obtain a CCM;
and arranging gas diffusion layers on two sides of the CCM to obtain the membrane electrode.
10. A fuel cell comprising the membrane electrode of claim 8 or the membrane electrode prepared according to claim 9.
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