CN111900420A - Anode catalyst slurry, anode catalyst layer, membrane electrode and fuel cell - Google Patents
Anode catalyst slurry, anode catalyst layer, membrane electrode and fuel cell Download PDFInfo
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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
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0656—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by electrochemical means
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
Abstract
The invention relates to anode catalyst slurry, an anode catalyst layer, a membrane electrode and a fuel cell. Relates to the technical field of fuel cells. The main technical scheme adopted is as follows: an anode catalyst slurry for preparing an anode catalyst layer of a fuel cell, wherein the anode catalyst slurry comprises a catalyst slurry body and an electrolyzed water catalyst. 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 electrolyzed water catalyst is used for catalyzing the electrolyzed water reaction; wherein the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal. The anode catalyst layer is obtained by coating the anode catalyst slurry on a proton exchange membrane and drying. A membrane electrode includes the above-described anode catalyst layer. The invention is mainly used for improving the anti-reversal performance of the membrane electrode in the fuel cell and solving the problem of membrane electrode damage caused by voltage reversal due to insufficient supply of anode fuel.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to anode catalyst slurry, an anode 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. A Membrane Electrode Assembly (MEA) is the core component of a proton exchange membrane fuel cell. The membrane electrode is composed of an anode gas diffusion layer, an anode catalyst layer, a 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 therefore, the preparation of a high-performance and high-power membrane electrode is of great significance to the commercialization of the fuel cell.
The catalyst layers (anode catalyst layer, cathode catalyst layer) of the membrane electrode are the sites where chemical reactions take place, and usually consist of a noble metal catalyst (e.g., Pt/C) and an ionomer (e.g., Nafion), where the carbon-supported catalyst particles achieve conduction of electrons and the ionomer is responsible for conduction of protons, which together form a complex network porous structure capable of conducting reaction gases and water.
In the reliable operation of the proton exchange membrane type fuel cell as an engine, when the engine is started/stopped, the air/oxygen or anode fuel (hydrogen) is not supplied to the cathode part of the fuel cell, and particularly when the hydrogen is supplied to the anode part, the potential of the anode part changes, and H is generated by the reaction of the electrolyzed water+To compensate for H at the anode+The reaction (1) is carried out: 2H2O＝4H++O2+4e-. If the reaction continues, reaction (2) will occur when the moisture content of the anode is too low: c +2H2O＝CO2+4H++4e-And reaction (3): c + H2O＝CO+2H++4e-(ii) a While also generating more heat. Although the reaction (2) and the reaction (3) should occur first in terms of thermodynamics, the reaction (1) is often dominant in actual operation because the kinetics of the reaction (1) dominate. When the reaction (1) is not easy to occur, the occurrence of the reaction (2) and the reaction (3) can cause damage to a catalyst layer of the membrane electrode and even a bipolar plate, and meanwhile, accumulated heat can easily cause pinholes to appear in the membrane electrode, so that short circuit occurs.
The fuel cell engine is inevitably started/stopped and accelerated/decelerated several times during operation, so that a shortage of hydrogen gas is inevitable. Therefore, in the case where the anode fuel supply is insufficient, a problem that the membrane electrode is damaged by voltage reversal (reverse polarity) easily occurs.
Disclosure of Invention
In view of the above, the present invention provides an anode catalyst slurry, an anode catalyst layer, a membrane electrode and a fuel cell, and mainly aims to solve the problem of membrane electrode damage caused by voltage reversal due to insufficient anode fuel supply.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, embodiments of the present invention provide an anode catalyst slurry for preparing an anode catalyst layer of a fuel cell, wherein the anode 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 electrolytic water catalyst is used for catalyzing the electrolytic water reaction; wherein the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the electrolytic water catalyst adopts RuO2、IrO2、RhO2One or more of; and/or the electrolyzed water catalyst is a nanoparticle.
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 mass percentage of the noble metal is 10-80%.
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 (i.e., I/C ratio) of the ionomer 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 anode catalyst slurry is 1-30 wt%; preferably, the solvent is an alcohol solvent.
In another aspect, an embodiment of the present invention further provides a method for preparing the anode catalyst slurry, where the method includes:
mixing the raw material of the catalyst slurry body with an electrolyzed water catalyst, 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 electrolyzed water catalyst, performing dispersion treatment to obtain anode 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 an anode catalyst layer, wherein the anode catalyst layer contains a carbon-supported noble metal catalyst and an electrolyzed water catalyst; wherein the carbon-supported noble metal catalyst comprises a carbon support and a noble metal supported on the carbon support; the electrolyzed water catalyst is used for catalyzing the electrolyzed water reaction, and the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal.
Preferably, the anode 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 anode catalyst layer is obtained by coating the anode catalyst slurry described above on a proton exchange membrane and drying the coating. 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 anode catalyst layer.
In another aspect, an embodiment of the present invention further provides a method for preparing the membrane electrode, where the method includes the following steps:
coating any one of the anode catalyst slurry on one side of a proton exchange membrane to form an anode catalyst layer, and coating the cathode catalyst slurry on the other side of the proton exchange membrane to form a cathode catalyst layer, thereby obtaining CCM (catalyst/proton exchange membrane module prepared by coating fuel cell catalysts on two sides of the proton exchange membrane, which 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 yet another aspect, embodiments of the present invention further provide a fuel cell, wherein the fuel cell includes a membrane electrode; wherein the membrane electrode is the membrane electrode; or the membrane electrode is prepared by the membrane electrode preparation method.
Compared with the prior art, the anode catalyst slurry, the anode catalyst layer, the membrane electrode and the fuel cell have the following beneficial effects:
the anode catalyst slurry and the preparation method thereof provided by the embodiment of the invention are characterized in that a set amount of electrolyzed water catalyst is added into a catalyst slurry body (namely, the existing catalyst slurry); thus, in a membrane electrode and a fuel cell including an anode catalyst layer prepared from the anode catalyst slurry, when hydrogen gas is insufficiently supplied, the electrolyzed water catalyst promotes the electrolyzed water reaction to produce H+To compensate for H at the anode+The oxidation corrosion reaction of carbon of the carbon carrier is avoided, so that the anti-reversal performance of the fuel cell is improved, and the damage of the membrane electrode is avoided. And, compared with the direct preparation of PtRuO2catalyst/C, PtIrO2In the case of the/C catalyst (i.e., after chemical reaction and heat treatment of the Pt/C catalyst, RuO can be loaded thereon2、IrO2The process is relatively complex), the invention is to add the electrolyzed water catalyst such as RuO directly into the catalyst slurry bulk2、IrO2、RhO2And the process is simple and the preparation cost is low. Here, by controlling the mass of the electrolyzed water catalyst to 20 to 100% of the mass of the noble metal in the carbon-supported noble metal catalyst, the electrical conductivity of the anode catalyst layer is not lowered, and the large ohmic polarization of the single cell is not caused.
In addition, the anode catalyst layer, the membrane electrode and the fuel cell provided by the embodiment of the invention adopt the anode catalyst slurry, so that the anode catalyst layer, the membrane electrode and the fuel cell have the beneficial effects, and repeated description is omitted.
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 showing the cell voltage changes of the membrane electrodes prepared in examples 1, 2, 3 and 4 according to the present invention and the membrane electrodes prepared in comparative examples 1, 2 and 3 according to comparative examples after different reverse polarity times, respectively (test conditions: hydrogen-air cell temperature of 70 ℃, cathode-anode back pressure of 30psi and relative humidity of 100%).
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 order to promote the water electrolysis reaction to generate H when the hydrogen supply is insufficient for the membrane electrode and the fuel cell+To compensate for H at the anode+The oxidation corrosion reaction of carbon of the carbon carrier is avoided, so that the anti-reversal performance of the fuel cell is improved, and the damage of the membrane electrode is avoided. To this end, embodiments of the present invention incorporate an electrolyzed water catalyst, such as RuO, in the anode catalyst layer of the membrane electrode2、IrO2、RhO2Etc. to promote the electrolytic water reaction when the hydrogen gas supply is insufficient. However, if PtRuO is prepared directly2catalyst/C, PtIrO2The process of the/C catalyst is complex, the cost is high, and the RuO can be loaded on the Pt/C catalyst after the Pt/C catalyst is subjected to chemical reaction and heat treatment2、IrO2。
Based on the problems, the invention provides the following technical scheme, which not only improves the anti-reversal performance of the fuel cell, but also has simple process.
In one aspect, embodiments of the present invention provide an anode catalyst paste for preparing an anode catalyst layer of a fuel cell, wherein the anode catalyst paste includes a catalyst paste bulk (i.e., an existing catalyst paste) and an electrolyzed water catalyst. The catalyst slurry body includes a carbon-supported noble metal catalyst. The catalyst for electrolyzing water is RuO2、IrO2、RhO2The particle size is nano-scale, and the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal in the carbon-supported noble metal catalyst.
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 mass content of the noble metal is 10-80%.
Preferably, in the carbon-supported noble metal catalyst, 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 catalyst slurry body also contains an ionic polymer, wherein the ionic polymer refers to perfluorosulfonic acid resin containing sulfonic acid groups and having proton exchange capacity; for example, when preparing the anode 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 anode catalyst slurry is 1-30 wt%; the solvent is an alcohol solvent, preferably isopropanol.
Here, the method for preparing the anode catalyst slurry includes the steps of: adding an ionic polymer into a solvent, uniformly dispersing, adding a carbon-supported noble metal catalyst and an electrolyzed water catalyst, and performing any one of ultrasonic (ultrasonic), ball milling and mechanical shearing (a homogenizer) to obtain uniformly dispersed 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 an anode catalyst layer, wherein the anode catalyst layer contains a carbon-supported noble metal catalyst, an ionic polymer and an electrolyzed water catalyst; the carbon-supported noble metal catalyst comprises a carbon carrier and noble metal supported on the carbon carrier; the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal. Wherein the anode catalyst layer is formed by coating the anode catalyst slurry on the proton exchange membrane (preferably, the loading amount of the noble metal in the anode catalyst layer is 0.05-0.3 mg/cm)2) 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 anode catalyst layer. Preferably, the membrane electrode comprises a CCM and gas diffusion layers positioned at both 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 anode catalyst slurry on one side of a proton exchange membrane to form an anode catalyst layer, and coating the cathode catalyst slurry on the other side of the proton exchange membrane to form a cathode 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) And arranging gas diffusion layers on two sides of the CCM to obtain the 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 following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications.
Example 1
Preparing anode catalyst slurry: a Pt/C catalyst with 70 percent of Pt by mass and RuO2Mixing the nano powder, perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent, and dispersing the mixture into anode catalyst slurry by ultrasonic waves. Wherein, in the anode catalyst slurry: RuO2The nano powder is 80% of the Pt mass in the Pt/C catalyst, the I/C ratio is 1:1 (the mass ratio of the ionic polymer to the carbon carrier is I/C ratio), and the solid content is 2 wt%.
Preparing cathode catalyst slurry: mixing a Pt/C catalyst with the Pt mass percentage of 70%, 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 I/C ratio was 1:1 and the solids content was 2% by weight.
Preparing a membrane electrode: according to the loading amount of Pt in the anode catalyst layer of 0.1mg/cm2The loading capacity of the cathode catalyst layer Pt is 0.4mg/cm2Respectively spraying anode catalyst slurry and cathode catalyst slurry on two sides of a Nafion211 proton exchange membrane by ultrasonic waves to form CCM, wherein the area of an active area is 5cm multiplied by 5cm, and attaching gas diffusion layers (SGL company) of 5cm multiplied by 5cm on two sides of the CCM to obtain the membrane electrode.
Activation conditions and polarization test conditions: in order to test the anti-reversal performance of the catalyst layer, the membrane electrode is placed in a single cell, activation treatment is carried out for 2 hours under the conditions that the temperature of the cell is 70 ℃ and the cathode and the anode are completely humidified, discharge is repeatedly carried out to fully activate the membrane electrode, and the cell performance test conditions are 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 cathode and the anode are in phaseThe relative humidity is 100 percent and is 1A/cm2Testing the voltage of the single cell at the current density of (a); then the hydrogen gas of the fuel gas was changed to nitrogen gas at 200mA/cm2After 30 minutes at the current density of (1A/cm), the nitrogen gas on the fuel gas side was replaced with hydrogen gas2Testing the voltage of the single cell at the current density of (a); this was repeated 4 times for a total of 120 minutes.
Example 2
Example 2 differs from example 1 in that: the preparation steps of the anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in example 2 was prepared as follows:
preparing anode catalyst slurry: a Pt/C catalyst with 70 percent of Pt by mass and IrO2Mixing the nano powder, perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent, and performing ball milling to disperse the mixture into anode catalyst slurry. Wherein, in the anode catalyst slurry: IrO2The nano powder accounts for 20% of the Pt mass 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 anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in example 3 was prepared as follows:
preparing anode catalyst slurry: mixing Pt/C catalyst with Pt content of 70% by mass and RhO2The nanopowder, perfluorosulfonic acid ionomer solution (5 wt% Nafion, Chemours corporation), and isopropanol solvent were mixed and dispersed into anode catalyst slurry by a homogenizer. In the anode catalyst slurry: RhO2The nano powder accounts for 60 percent of the mass of Pt in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 weight percent.
Example 4
Example 4 differs from example 1 in that: the preparation steps of the anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in example 4 was prepared as follows:
a Pt/C catalyst with 70 percent of Pt by mass and RuO2Nanopowder, RhO2Nano powderAnd mixing the powder with a perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours) and isopropanol serving as a solvent, and dispersing the mixture by ultrasonic waves to obtain anode catalyst slurry. Wherein, in the anode catalyst slurry: RuO2The nano powder accounts for 50 percent of the mass of Pt in the Pt/C catalyst and accounts for RhO2The nano powder accounts for 50% of the weight of Pt in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
Comparative example 1
Comparative example 1 differs from example 1 in that: the preparation steps of the anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in comparative example 1 was prepared as follows:
mixing a Pt/C catalyst with the Pt mass percentage of 70%, a perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent, and dispersing the mixture into anode catalyst slurry by ultrasonic waves. Wherein, in the anode 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 anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in comparative example 2 was prepared as follows:
a Pt/C catalyst with 70 percent of Pt by mass and RuO2Mixing the nano powder, perfluorinated sulfonic acid ionic polymer solution (5 wt% Nafion, Chemours company) and isopropanol serving as a solvent, and dispersing the mixture into anode catalyst slurry by ultrasonic waves. Wherein, in the anode catalyst slurry: RuO2The nano powder accounts for 10 percent of the mass of Pt in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 weight percent.
Comparative example 3
Comparative example 3 differs from example 1 in that: the preparation steps of the anode catalyst slurry are different, and the rest steps are consistent. The anode catalyst slurry in comparative example 3 was prepared as follows:
Pt/C catalyst with 70 percent of Pt by mass, IrO2 nano powder, perfluorinated sulfonic acid ionic polymer solution (5 percent by weight of Nafion, Chemours company) and isopropanol solvent are mixed and dispersed into anode catalyst slurry by a homogenizer. At the anode is catalyzedIn the slurry: IrO2The nano powder accounts for 150% of the mass of Pt in the Pt/C catalyst, the I/C ratio is 1:1, and the solid content is 2 wt%.
As shown in FIG. 1, in each of examples 1, 2, 3 and 4, RuO with a mass percentage of 80% of the mass of Pt was added to the anode catalyst layer220% of IrO260% of RhO250% RuO2+ 50% of RhO2And testing the voltage curve of the single cell after the single cell is subjected to polarity reversal for 30min, 60min, 90min and 120 min. Comparative example 1 is 1A/cm after reversal of the polarity of a single cell without an electrolyzed water catalyst2Cell voltage at current density. Comparative examples 2 and 3 were each an anode catalyst layer to which RuO was added in an amount of 10% by mass based on Pt mass2150% IrO2And the single cell voltage curves of the manufactured single cell are tested after the pole reversal is carried out for 30min, 60min, 90min and 120min respectively.
As can be seen from fig. 1: (1) the initial voltage of the unit cell without the electrolytic water catalyst in comparative example 1 (when the anti-reverse polarity is not made) was the highest, but the anti-reverse polarity time was too short. (2) The mass of the catalyst added into the electrolyzed water in the embodiments 1, 2, 3 and 4 is 20-100% of the mass of Pt, and after 120min reversal, the single cell is at 1A/cm2Under the current density, the voltage is reduced within 10 percent, and the anti-reversal performance is good. (3) In comparative example 2, because the addition amount of the electrolyzed water catalyst is too small and is only 10% of the mass of Pt, after 120min of reversal, the voltage of a single cell is reduced by 25%, and the anti-reversal performance is poor. (4) IrO was added in an amount of 150% by mass based on Pt in comparative example 32Although the single cell of (2) has good anti-reversal performance and the voltage reduction is within 10%, the initial voltage (when no anti-reversal is made) is the lowest because the electrolytic water catalyst is oxide, the addition amount is too much, the conductivity is deteriorated, and the ohmic polarization of the single cell is large and is 1A/cm2The cell voltage at current density is low.
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. An anode catalyst slurry for use in preparing an anode catalyst layer of a fuel cell, the anode 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 electrolytic water catalyst is used for catalyzing the electrolytic water reaction; wherein the mass of the electrolyzed water catalyst is 20-100% of the mass of the noble metal.
2. The anode catalyst ink according to claim 1, wherein said electrolyzed water catalyst is RuO2、IrO2、RhO2One or more of; and/or
The electrolytic water catalyst is a nanoparticle.
3. The anode catalyst slurry 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 mass percentage of the noble metal is 10-80%.
4. The anode catalyst slurry 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.
5. The anode catalyst slurry according to any one of claims 1 to 4,
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; and/or
The catalyst slurry body also contains a solvent; wherein the solid content of the anode catalyst slurry is 1-30 wt%; preferably, the solvent is an alcohol solvent.
6. The method for preparing an anode catalyst slurry according to any one of claims 1 to 5, characterized by comprising the steps of:
mixing the raw material of the catalyst slurry body with an electrolyzed water catalyst, 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 electrolyzed water catalyst, performing dispersion treatment to obtain anode catalyst slurry;
preferably, the dispersion treatment is one or more of ultrasonic treatment, ball milling treatment and mechanical shearing treatment.
7. An anode catalyst layer, characterized in that the anode catalyst layer contains a carbon-supported noble metal catalyst and an electrolyzed water catalyst; wherein the carbon-supported noble metal catalyst comprises a carbon support and a noble metal supported on the carbon support; the electrolytic water catalyst is used for catalyzing electrolytic water reaction, and the mass of the electrolytic water catalyst is 20-100% of that of the noble metal;
preferably, the anode 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 anode catalyst layer is obtained by coating the anode catalyst slurry according to any one of claims 1 to 5 on a proton exchange membrane and drying the coating.
8. A membrane electrode, wherein the membrane electrode comprises the anode catalyst layer of claim 7.
9. The method for preparing a membrane electrode according to claim 8, characterized in that it comprises the steps of:
applying the anode catalyst ink of any one of claims 1-5 to one side of a proton exchange membrane to form an anode catalyst layer and applying the cathode catalyst ink to the other side of the proton exchange membrane to form a cathode 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, characterized in that the fuel cell comprises a membrane electrode; wherein the content of the first and second substances,
the membrane electrode is the membrane electrode of claim 8; or the membrane electrode is a membrane electrode prepared by the membrane electrode preparation method according to claim 9.
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| CN112993284A (en) * | 2021-02-04 | 2021-06-18 | 上海亿氢科技有限公司 | Water electrolysis catalyst layer and manufacturing method thereof |
| CN113178582A (en) * | 2021-03-26 | 2021-07-27 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell anti-reversal electrode PtIr/CNT catalyst and preparation method thereof |
| CN113522206A (en) * | 2021-08-03 | 2021-10-22 | 湖南新欧源环保科技有限公司 | Multi-ion hydrolysis blue oxygen generator assembly |
| CN113629255A (en) * | 2021-06-29 | 2021-11-09 | 东风汽车集团股份有限公司 | Anti-reversal catalyst for battery and preparation method and application thereof |
| CN113745545A (en) * | 2021-08-31 | 2021-12-03 | 上海氢晟新能源科技有限公司 | Anti-reversal treatment method for membrane electrode in fuel cell stack |
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| CN114196990A (en) * | 2021-10-08 | 2022-03-18 | 鸿基创能科技(广州)有限公司 | Cathode catalyst slurry for proton exchange membrane water electrolysis device and preparation method thereof |
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| CN112993284A (en) * | 2021-02-04 | 2021-06-18 | 上海亿氢科技有限公司 | Water electrolysis catalyst layer and manufacturing method thereof |
| CN113178582A (en) * | 2021-03-26 | 2021-07-27 | 中国科学院大连化学物理研究所 | Proton exchange membrane fuel cell anti-reversal electrode PtIr/CNT catalyst and preparation method thereof |
| CN113629255A (en) * | 2021-06-29 | 2021-11-09 | 东风汽车集团股份有限公司 | Anti-reversal catalyst for battery and preparation method and application thereof |
| CN113522206A (en) * | 2021-08-03 | 2021-10-22 | 湖南新欧源环保科技有限公司 | Multi-ion hydrolysis blue oxygen generator assembly |
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| CN113871629A (en) * | 2021-09-28 | 2021-12-31 | 中汽创智科技有限公司 | Anti-reversal catalyst, preparation method and application thereof |
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| CN114512688A (en) * | 2021-12-27 | 2022-05-17 | 安徽明天新能源科技有限公司 | CCM for fuel cell membrane electrode and production method thereof |
| CN114420944A (en) * | 2022-01-19 | 2022-04-29 | 一汽解放汽车有限公司 | Fuel cell membrane electrode, preparation method thereof and fuel cell |
| CN114420944B (en) * | 2022-01-19 | 2024-02-23 | 一汽解放汽车有限公司 | Fuel cell membrane electrode, preparation method thereof and fuel cell |
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| CN114899430B (en) * | 2022-04-07 | 2023-09-19 | 安徽明天氢能科技股份有限公司 | Fuel cell CCM with high durability and anti-counter pole and preparation method thereof |
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