CN118800919B - Fuel cell double catalytic layer cathode, preparation method and fuel cell - Google Patents
Fuel cell double catalytic layer cathode, preparation method and fuel cell Download PDFInfo
- Publication number
- CN118800919B CN118800919B CN202411281684.7A CN202411281684A CN118800919B CN 118800919 B CN118800919 B CN 118800919B CN 202411281684 A CN202411281684 A CN 202411281684A CN 118800919 B CN118800919 B CN 118800919B
- Authority
- CN
- China
- Prior art keywords
- catalytic layer
- fuel cell
- cathode
- catalytic
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M4/8605—Porous electrodes
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
Abstract
本发明涉及燃料电池领域，具体而言，提供了一种燃料电池双催化层阴极、制备方法及燃料电池。所述燃料电池双催化层阴极包括用于设置在质子交换膜一侧的第一催化层和用于设置在气体扩散层一侧的第二催化层；所述第一催化层和所述第二催化层各自独立地为基于碳载体的铂钴合金催化层；所述第一催化层比表面积为500~900 m2/g，二次孔隙尺寸为20~50nm；所述第二催化层比表面积为50~150 m2/g，二次孔隙尺寸为70~100nm。本发明可兼顾燃料电池阴极催化层的传质能力和保水能力。
The present invention relates to the field of fuel cells, and in particular, provides a fuel cell double-catalyst layer cathode, a preparation method and a fuel cell. The fuel cell double-catalyst layer cathode comprises a first catalytic layer for being arranged on one side of a proton exchange membrane and a second catalytic layer for being arranged on one side of a gas diffusion layer; the first catalytic layer and the second catalytic layer are each independently a platinum-cobalt alloy catalytic layer based on a carbon carrier; the first catalytic layer has a specific surface area of 500-900 m2 /g and a secondary pore size of 20-50nm; the second catalytic layer has a specific surface area of 50-150 m2 /g and a secondary pore size of 70-100nm. The present invention can take into account both the mass transfer capacity and water retention capacity of the fuel cell cathode catalytic layer.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a double-catalytic-layer cathode of a fuel cell, a preparation method and the fuel cell.
Background
The platinum-cobalt alloy catalyst has excellent catalytic activity due to the synergistic effect of platinum and cobalt, and can accelerate the progress of key reactions in the fuel cell, thereby effectively improving the power density and the energy conversion efficiency of the fuel cell. In addition, the platinum-cobalt catalyst also helps to reduce the use amount of noble metal platinum, thereby reducing the cost of the fuel cell and providing powerful support for commercial application of the fuel cell. However, low humidity or non-humidified operating conditions can result in reduced ionic conductivity and increased ohmic losses in the catalytic layer and proton exchange membrane, further exacerbating performance losses. In general, it is necessary to humidify the fuel cell, but this increases the cost of the fuel cell system. In addition, the water management in the fuel cell is particularly important under high current density, and the too high water content can cause liquid water to block the pore structure of the catalytic layer, so that the mass transfer capacity is greatly reduced, and the improvement of the performance of the fuel cell is restricted. Therefore, the mass transfer capability and the water retention capability of the cathode catalytic layer of the fuel cell are both significant.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a double-catalytic-layer cathode of a fuel cell, a preparation method and the fuel cell, so as to solve the problem that the mass transfer capacity and the water retention capacity of the cathode catalytic layer of the fuel cell cannot be considered in the prior art.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
In a first aspect, the present invention provides a fuel cell dual catalytic layer cathode comprising a first catalytic layer for placement on one side of a proton exchange membrane and a second catalytic layer for placement on one side of a gas diffusion layer;
The first catalytic layer and the second catalytic layer are respectively and independently platinum-cobalt alloy catalytic layers based on carbon carriers, the specific surface area of the first catalytic layer is 500-900 m 2/g, the secondary pore size is 20-50 nm, the specific surface area of the second catalytic layer is 50-150 m 2/g, and the secondary pore size is 70-100 nm.
As a further preferable embodiment, the carbon support includes acetylene black, ketjen black or conductive carbon black.
As a further preferable technical scheme, the Pt loading in the cathode is 0.1-0.3 mg/cm 2.
In a second aspect, the present invention provides a method for preparing the cathode with double catalytic layers for a fuel cell, comprising the following steps:
Uniformly mixing a carbon carrier, water, a platinum source and a cobalt source to obtain a platinum-cobalt precursor aqueous solution;
transferring the platinum cobalt precursor aqueous solution into rotary steaming equipment for steaming and drying treatment;
Roasting the powder obtained by evaporation in inert atmosphere, and carrying out acid washing and drying to obtain a platinum-cobalt alloy catalyst based on a carbon carrier;
Uniformly mixing the platinum-cobalt alloy catalyst based on the carbon carrier, water, an organic solvent and an ionomer solution to obtain a first catalytic layer ink and a second catalytic layer ink respectively;
And spraying the first catalytic layer ink and the second catalytic layer ink on the proton exchange membrane in sequence to obtain the fuel cell double-catalytic-layer cathode.
According to a further preferable technical scheme, the method is carried out under a sealed condition when a carbon carrier, water, a platinum source and a cobalt source are mixed, the stirring speed is 300-500 rpm, the stirring temperature is 25-35 ℃, the stirring time is 12-36 h, and the concentration of the platinum cobalt precursor aqueous solution is 3-3.5 g/L.
As a further preferable technical scheme, the rotation speed of the rotary steaming device is 100-150 rpm, the evaporation temperature is 50-60 ℃, and the vacuum condition is one atmosphere.
As a further preferable technical scheme, the roasting temperature is 500-800 ℃, the roasting time is 2-6 h, and 0.5-1M acid solution and water are adopted for washing in sequence during acid washing.
As a further preferable technical scheme, when the platinum-cobalt alloy catalyst based on the carbon carrier, water, an organic solvent and an ionomer solution are mixed, the concentration of the mixed solution is 4-8 mg/mL, the mixing mode is ultrasonic dispersion, and the ionomer content accounts for 10-30 wt% of the total mass of the solid material.
As a further preferable technical scheme, the spraying temperature is 70-90 ℃.
In a third aspect, the present invention provides a fuel cell, including the above-mentioned fuel cell double-catalytic-layer cathode, or a fuel cell double-catalytic-layer cathode prepared by adopting the above-mentioned preparation method of fuel cell double-catalytic-layer cathode.
Compared with the prior art, the invention has the beneficial effects that:
The fuel cell double-catalytic-layer cathode provided by the invention has a secondary pore gradient from the proton exchange membrane to the gas diffusion layer, is beneficial to gas-liquid two-phase flow under high current density, and optimizes water management and mass transfer capacity under high load. The first catalytic layer near the proton exchange membrane side has a higher specific surface area, can store partial water generated by reaction in the operation process of the fuel cell, is favorable for maintaining the hydration of the proton exchange membrane and the ion conductivity of the catalytic layer under the condition that the cathode is not humidified, and weakens the performance attenuation of the fuel cell under the extreme operation working condition.
Drawings
FIG. 1 is a graph showing the pore size distribution of the catalyst measured by the full-automatic specific surface analyzer and fitted in example 1.
FIG. 2 shows the pore size distribution of the catalytic layer measured by mercury porosimetry and fitted in example 1.
Fig. 3 (a) is a polarization curve and a power density curve measured under the condition of full humidification of the cathode double catalytic layer and the cathode of the conventional single-layer cathode catalytic layer in example 1.
Fig. 3 (b) is a polarization curve and a power density curve measured in example 1 under the condition that the cathode of the cathode double catalytic layer is not humidified compared with the cathode of the conventional single-layer cathode catalytic layer.
FIG. 4 shows the results of electrochemical impedance testing for different relative humidity at current densities of cathode bi-catalytic layer 2A/cm 2 in example 1.
Fig. 5 (a) shows pore size distribution of the catalyst obtained by measurement using a fully automatic specific surface analyzer and fitting in example 2.
Fig. 5 (b) shows the pore size distribution of the catalytic layer obtained by measurement by mercury intrusion and fitting in example 2.
Fig. 6 (a) is a pore size distribution of the catalyst measured using a fully automatic specific surface analyzer and fitted in example 3.
Fig. 6 (b) shows pore size distribution of the catalytic layer obtained by measurement by mercury intrusion and fitting in example 3.
Fig. 7 (a) is a polarization curve and a power density curve measured under the full humidification condition after the catalyst layer sequence is adjusted in comparative example 2 and example 1.
FIG. 7 (b) is a graph showing the polarization curve and the power density curve measured in comparative example 2 in example 1 and in the condition of no humidification after the adjustment of the order of the catalytic layers.
FIG. 7 (c) is a graph showing the results of the electrochemical impedance test under the current density of 2A/cm 2 measured under the full humidification condition after the catalyst layer sequence was adjusted in comparative example 2.
FIG. 7 (d) is a graph showing the results of the electrochemical impedance test of comparative example 2 at a current density of 2A/cm 2 measured in the absence of humidification after the catalytic layer sequence was adjusted in example 1.
Fig. 8 (a) is a polarization curve and a power density curve measured under the condition of full humidification of the mixed catalyst layer in comparative example 3, example 1.
Fig. 8 (b) is a polarization curve and a power density curve measured under the condition of full humidification of the mixed catalyst layer in comparative example 3, example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer.
As one aspect of the present invention, there is provided a fuel cell dual catalytic layer cathode comprising a first catalytic layer for being disposed on one side of a proton exchange membrane and a second catalytic layer for being disposed on one side of a gas diffusion layer;
The first catalytic layer and the second catalytic layer are respectively and independently platinum-cobalt alloy catalytic layers based on carbon carriers, the specific surface area of the first catalytic layer is 500-900 m 2/g, the secondary pore size is 20-50 nm, the specific surface area of the second catalytic layer is 50-150 m 2/g, and the secondary pore size is 70-100 nm.
The specific surface area of the first catalytic layer is typically, but not limited to, 500, 550, 600, 650, 700, 750, 800, 850 or 900 m 2/g, preferably 700-900 m 2/g. The secondary pore size of the first catalytic layer is typically, but not limited to, 20, 30, 40 or 50nm. The specific surface area of the second catalytic layer is typically, but not limited to, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150 m 2/g, preferably 50-120 m 2/g. The secondary pore size of the first catalytic layer is typically, but not limited to, 70, 80, 90 or 100nm.
The cathode of the fuel cell double catalytic layer has a secondary pore gradient from the proton exchange membrane to the gas diffusion layer, is beneficial to gas-liquid two-phase flow under high current density, and optimizes water management and mass transfer capacity under high load. The first catalytic layer near the proton exchange membrane side has a higher specific surface area, can store partial water generated by reaction in the operation process of the fuel cell, is favorable for maintaining the hydration of the proton exchange membrane and the ion conductivity of the catalytic layer under the condition that the cathode is not humidified, and weakens the performance attenuation of the fuel cell under the extreme operation working condition.
In an alternative embodiment, the carbon support comprises acetylene black, ketjen black, or conductive carbon black.
In an alternative embodiment, the Pt loading in the cathode is 0.1-0.3 mg/cm 2. Pt loading in the cathode is typically, but not limited to, 0.1, 0.15, 0.2, 0.25 or 0.3mg/cm 2.
As another aspect of the present invention, the present invention provides a method for preparing a cathode for a fuel cell having a double catalytic layer, comprising the steps of:
Uniformly mixing a carbon carrier, water, a platinum source and a cobalt source to obtain a platinum-cobalt precursor aqueous solution;
transferring the platinum cobalt precursor aqueous solution into rotary steaming equipment for steaming and drying treatment;
Roasting the powder obtained by evaporation in inert atmosphere, and carrying out acid washing and drying to obtain a platinum-cobalt alloy catalyst based on a carbon carrier;
Uniformly mixing the platinum-cobalt alloy catalyst based on the carbon carrier, water, an organic solvent and an ionomer solution to obtain a first catalytic layer ink and a second catalytic layer ink respectively;
And spraying the first catalytic layer ink and the second catalytic layer ink on the proton exchange membrane in sequence to obtain the fuel cell double-catalytic-layer cathode.
Wherein, the above-mentioned "the first catalytic layer ink and the second catalytic layer ink are obtained respectively" means that the platinum cobalt alloy catalyst based on the carbon carrier in the first catalytic layer ink and the second catalytic layer ink are different, and thus the obtained inks are also different.
The preparation method is simple and easy to implement, the cost is low, the carbon carrier, water, chloroplatinic acid aqueous solution and cobalt nitrate hexahydrate are sequentially and uniformly mixed, and the catalyst material is obtained after evaporation and high-temperature reduction, and the material has a required structure, good conductivity and excellent oxygen reduction performance. The cathode catalytic layer prepared by spraying the catalytic layer ink can be firmly bonded on the proton exchange membrane, and is beneficial to effective proton conduction between the catalytic layer and the proton exchange membrane.
Optionally, the platinum source comprises one of chloroplatinic acid, platinum nitrate and potassium chloroplatinate, and the cobalt source comprises one of cobalt nitrate, cobalt chloride and cobalt carbonate.
In an alternative embodiment, the carbon carrier, the water, the platinum source and the cobalt source are mixed under a sealed condition, the stirring speed is 300-500 rpm, the stirring temperature is 25-35 ℃, the stirring time is 12-36 h, and the concentration of the platinum cobalt precursor aqueous solution is 3-3.5 g/L. The stirring speed is typically but not limited to 300, 350, 400, 450 or 500rpm, the stirring temperature is typically but not limited to 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35 ℃, the stirring time is typically but not limited to 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34 or 36 hours, preferably 18 to 24 hours, and the concentration of the platinum cobalt precursor aqueous solution is typically but not limited to 3, 3.1, 3.2, 3.3, 3.4 or 3.5 g/L.
In an alternative embodiment, the rotation speed of the rotary steaming device is 100-150 rpm, the evaporation temperature is 50-60 ℃, and the vacuum condition is one atmosphere. The above rotational speed is typically, but not limited to, 100, 110, 120, 130, 140 or 150rpm, and the evaporation temperature is typically, but not limited to, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or 60 ℃.
In an alternative embodiment, the roasting temperature is 500-800 ℃, the roasting time is 2-8 hours, and 0.5-1M acid solution and water are adopted for washing in sequence during acid washing. The above calcination temperatures are typically, but not limited to, 500, 600, 700 or 800 ℃, the calcination times are typically, but not limited to, 2,3, 4, 5, 6, 7, 8 hours, and the concentration of the acid solution is typically, but not limited to, 0.5, 0.75 or 1M. The acid solution may be sulfuric acid, nitric acid or hydrochloric acid solution.
Optionally, the acid-washed is dried by a vacuum drying oven, or by a forced air drying oven.
In an alternative embodiment, when the platinum-cobalt alloy catalyst based on the carbon carrier, water, an organic solvent and an ionomer solution are mixed, the concentration of the mixed solution is 4-8 mg/mL, the mixing mode is ultrasonic dispersion, and the ionomer content accounts for 10-30 wt% of the total mass of the solid material. The concentration of the above mixed solution is typically, but not limited to, 4, 5, 6, 7 or 8 mg/mL, and the ionomer content is typically, but not limited to, 10, wt%, 20, wt% or 30, wt% of the total mass of the solid material.
In this embodiment, the mixing mode of the platinum-cobalt alloy precursor solution is stirring, and the mixing mode of the catalytic layer ink is ultrasonic dispersion. Stirring is favorable for long-time mixing treatment, ultrasonic dispersion is high in efficiency in a short time, and the mixing effect is good.
Alternatively, the organic solvent is an alcohol, preferably isopropanol. Isopropyl alcohol is widely available, miscible with water, and has a suitable dielectric constant.
In an alternative embodiment, the spraying temperature is 70-90 ℃. The spray temperature is typically, but not limited to, 70, 80, or 90 ℃.
As another aspect of the invention, the invention also provides a fuel cell, which comprises the fuel cell double-catalytic-layer cathode, or the fuel cell double-catalytic-layer cathode prepared by adopting the preparation method of the fuel cell double-catalytic-layer cathode.
The fuel cell also comprises an anode, the anode is additionally prepared, the preparation method is the same as that of the cathode, the anode catalytic material is replaced by a commercial 20wt% Pt/C catalyst, the ionomer content is 10-30wt%, and the Pt load is about 0.1mgPt/cm 2.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
A fuel cell prepared by the method of:
100mg of acetylene black carbon carrier is weighed and immersed in 30mL of deionized water and 8.7mL of chloroplatinic acid solution (19.3 mmol/L), mixed and stirred for 10min, then 51.6mg of cobalt nitrate hexahydrate is added, and stirring is carried out overnight for 24h, and spin steaming treatment is adopted after uniform mixing. The rotation speed was chosen to be 150rpm and the evaporation temperature was 55 ℃. Transferring the obtained black powder into a high-temperature tube furnace, heating to 600 ℃ in a mixed gas of 95%vol argon and 5%vol hydrogen, calcining at high temperature for 6 hours, and naturally cooling to room temperature to obtain the platinum-cobalt alloy catalyst. Finally, the catalyst was washed with 0.5M sulfuric acid at 80℃for 8h to remove unstable cobalt species. The catalyst was then washed with deionized water until the filtrate ph=7. Transfer to a vacuum oven and dry overnight at 60℃and the catalyst obtained is designated PtCo/AB.
Another catalyst synthesis method is similar to the above, except that the carbon support is replaced with Ketjen black 600JD, and the catalyst obtained is designated PtCo/KB-600JD.
Mixing the obtained platinum cobalt alloy catalyst with Nafion solution (Dupon), deionized water and isopropanol, and performing ultrasonic treatment to prepare cathode platinum cobalt alloy catalyst ink. Wherein the concentration of the catalyst ink is 10 mg/mL, nafion accounts for 20wt% of the total solid mass, and the volume ratio of water to isopropanol is 1:4.
Mixing Pt/C catalyst (40%Pt,Johnson Matthey) catalyst with Nafion solution (Dupon), deionized water and isopropanol, and ultrasonically preparing anode platinum-carbon catalyst ink. Wherein the concentration of the catalyst ink is 10 mg/mL, nafion accounts for 25wt% of the total solid mass, and the volume ratio of water to isopropanol is 1:4.
One side of a Gore film (12 mu m, gore) is sprayed with Pt/C catalyst ink as an anode, the other side close to the film side is preferably coated with platinum cobalt alloy catalyst ink with ketjen black 600JD as a carbon carrier, and then is sprayed with platinum cobalt alloy catalyst ink with acetylene black as the carbon carrier as a cathode. Wherein the Pt loading in the anode catalytic layer is 0.1mg/cm 2, and the Pt loading in the cathode catalytic layer is 0.2mg/cm 2. The spray temperatures were all 80 ℃ (note that the platinum loadings of the two catalysts in the cathode catalytic layer were equally distributed)
After the catalytic layer is sprayed, carbon paper film forming electrodes are added to the anode and cathode, and then the fuel cell is assembled for testing. The test conditions are that the hydrogen flow rate is 300 mL/min, the air flow rate is 1500 mL/min, the back pressure is 100kPa, the test temperature is 80 ℃, the anode is 100% RH, and the two operation conditions of the cathode are respectively 0% RH and 100% RH.
All parameters in this example are within the preferred scope of the invention.
The nitrogen isothermal adsorption curve of the obtained platinum-cobalt alloy catalyst is measured by using a full-automatic specific surface analyzer, and the pore size distribution of the catalyst is obtained by fitting, as shown in figure 1, the pores in the catalyst taking acetylene black as a carbon carrier can be seen to consist of a small part of micropores with the diameter of 1-2nm and mesopores with the diameter of 2-3 nm. Calculated, the BET specific surface area is 55.1 m 2/g. The internal pore of the catalyst taking Ketjen black 600JD as a carbon carrier consists of a large number of micropores with the diameter of 1-2nm and mesopores with the diameter of 2-10 nm. Calculated, the BET specific surface area is 820 m 2/g.
The pore structure of the two catalytic layers was characterized using mercury intrusion, as shown in fig. 2. According to mercury intrusion analysis, the Pt-Co/AB catalytic layer provides continuous pore diameters in the range of 40-200 nm and the average pore diameter is about 95nm, which shows that the Pt-Co/AB catalytic layer is full of a larger secondary pore structure. The Pt-Co/KB-600JD catalytic layer curve has a typical flat profile, indicating that a catalyst with a high specific surface area and porous structure forms a catalytic layer with fewer and smaller secondary pore structures.
Fig. 3 (a) is a graph showing the measured polarization curve and power density curve, and the double catalytic layer cathode of this example increased the maximum power density of the fuel cell by 12.7% under the cathode full humidification condition compared to the conventional single cathode catalytic layer. This benefits from the optimization of mass transfer capacity resulting from the formation of a gradient structure that progressively enlarges the pores from the proton exchange membrane to the gas diffusion layer, resulting in a significant increase in peak power density. Fig. 3 (b) is a graph showing the measured polarization curve and power density curve, and the dual catalyst layer cathode of this example increases the maximum power density of the fuel cell by 20.2% in comparison with the conventional single cathode catalyst layer without humidification of the cathode. The increase in peak power density is not only due to the enhanced mass transfer properties due to the pore gradient of the cathode catalytic layer, but is also closely related to the "water storage" effect of the high specific surface area catalytic layer on the side close to the proton exchange membrane. The results of the electrochemical impedance test at a current density of 2A/cm 2 are shown in FIG. 4, and the high frequency resistance of the cathode double catalytic layer does not change significantly as the relative humidity decreases from 100% to 0% RH. The high specific surface area catalytic layer has water holding capacity, and can store partial water generated by reaction under the condition of no humidification, so that the proton conductivity of the proton exchange membrane and the cathode catalytic layer is not obviously reduced, the influence caused by ohmic loss is effectively relieved, and the performance of the fuel cell is maintained in a certain range.
Example 2
A fuel cell was different from example 1 in that acetylene black was replaced with XC-72 carbon support in this example, the catalyst obtained was designated PtCo/XC-72, pt/C catalyst ink was sprayed on one side of a Gore membrane (12 μm, gore) as an anode, platinum cobalt alloy catalyst ink with Ketjen black 600JD as a carbon support was preferably sprayed on the other side near the membrane side, and then platinum cobalt alloy catalyst ink with XC-72 as a carbon support was sprayed as a cathode.
The nitrogen isothermal adsorption curve of the obtained platinum cobalt alloy catalyst is measured by using a full-automatic specific surface analyzer, and the pore size distribution of the catalyst is obtained by fitting, as shown in fig. 5 (a), it can be seen that pores in the catalyst taking XC-72 as a carbon carrier consist of micropores of 1-2 nm. Calculated, the BET specific surface area is 140.1 m 2/g.
The pore structure of the above-described catalytic layer was characterized using mercury intrusion, as shown in fig. 5 (b). According to mercury intrusion analysis, the Pt-Co/XC-72 catalytic layer provides continuous pore diameters in the range of 20-200 nm, and the average pore diameter is about 65nm, which shows that the secondary pore gap of the Pt-Co/XC-72 catalytic layer is reduced compared with that of the Pt-Co/AB catalytic layer.
Using the polarization curve and power density measured in this example, the dual catalytic layer cathode in this example increased the maximum power density of the fuel cell by 5.8% under full cathode humidification compared to the conventional single cathode catalytic layer. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 13.7% without humidification of the cathode.
Example 3
A fuel cell was different from example 1 in that acetylene black was replaced with ketjen black 300J carbon support in this example, and another catalyst was a platinum cobalt alloy catalyst using acetylene black as a carbon support. During spraying, one side of a Gore film (12 mu m, gore) is sprayed with Pt/C catalyst ink as an anode, the other side of the Gore film, which is close to the film side, is preferably coated with platinum-cobalt alloy catalyst ink with ketjen black 300J as a carbon carrier, and then is sprayed with platinum-cobalt alloy catalyst ink with acetylene black as the carbon carrier as a cathode.
The nitrogen isothermal adsorption curve of the obtained platinum-cobalt alloy catalyst is measured by using a full-automatic specific surface analyzer, and the pore size distribution of the catalyst is obtained by fitting, as shown in fig. 6 (a), it can be seen that the pores in the catalyst taking ketjen black 300J as a carbon carrier consist of micropores of 1-2nm and mesopores of 2-3 nm. Calculated, the BET specific surface area is 750 m 2/g.
The pore structure of the above-described catalytic layer was characterized using mercury intrusion, as shown in fig. 6 (b). According to mercury intrusion analysis, the Pt-Co/XC-72 catalytic layer provides continuous pore diameters in the range of 10-200 nm, and the average pore diameter is about 30nm, again indicating that catalysts with high specific surface area and porous structure tend to form catalytic layers with less and smaller secondary pore structures.
Using the polarization curve and power density measured in this example, the dual catalytic layer cathode in this example increased the maximum power density of the fuel cell by 8.2% under full cathode humidification compared to the conventional single cathode catalytic layer. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 9.6% without humidification of the cathode.
Example 4
A fuel cell was different from example 1 in that Nafion was 20wt% of the solid mass of the platinum cobalt alloy catalyst using acetylene black as a carbon support, and Nafion was 30wt% of the solid mass of the platinum cobalt alloy catalyst using ketjen black 600JD as a carbon support.
Using the polarization curve and power density measured in this example, the maximum power density of the fuel cell was increased by 9.4% at 100% rh for the cathode and 16.4% for the cathode without humidification for the dual catalytic layer cathode in this example, due to the high ionomer content near the membrane side optimizing proton conductivity of the proton exchange membrane and hydration capacity of the catalytic layer.
Example 5
A fuel cell was different from example 1 in that Nafion was 20wt% of the solid mass of the platinum cobalt alloy catalyst using acetylene black as a carbon support, and Nafion was 10wt% of the solid mass of the platinum cobalt alloy catalyst using ketjen black 600JD as a carbon support.
Using the polarization curve and power density measured in this example, the maximum power density of the fuel cell was increased by 7% at 100% rh for the cathode and 13.7% for the cathode without humidification for the dual catalytic layer cathode in this example, due to the high ionomer content near the membrane side optimizing proton conductivity of the proton exchange membrane and hydration capacity of the catalytic layer.
Example 6
A fuel cell was different from example 1 in that Nafion was 30wt% of the solid mass of the platinum cobalt alloy catalyst using acetylene black as a carbon support, and Nafion was 20wt% of the solid mass of the platinum cobalt alloy catalyst using ketjen black 600JD as a carbon support.
By using the polarization curve and the power density measured in this example, the maximum power density of the fuel cell is increased by 2.3% under the cathode full humidification condition by the double-catalytic-layer cathode in this example, and the secondary pore structure of the catalytic layer near one side of the gas diffusion layer is reduced due to the increase of the ionomer content, so that the mass transfer capability is reduced under the high current density condition. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 13.7% without humidification of the cathode.
Example 7
A fuel cell was different from example 1 in that Nafion was 10wt% of the solid mass of the platinum cobalt alloy catalyst using acetylene black as a carbon support, and Nafion was 20wt% of the solid mass of the platinum cobalt alloy catalyst using ketjen black 600JD as a carbon support.
With the polarization curve and the power density measured in this example, the cathode with the double catalytic layers in this example increases the maximum power density of the fuel cell by 10.5% under the cathode full humidification condition, and the reduction of the ionomer content slightly increases the secondary pore structure of the catalytic layer near the gas diffusion layer side compared with the optimum ionomer content, but the reduction of the ionomer content reduces the proton conductivity of the catalytic layer, and the performance is reduced. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 15.6% without humidification of the cathode.
Example 8
Unlike example 1, in this example, the Pt loading in the anode catalytic layer was 0.1mg/cm 2, and the Pt loading in the cathode catalytic layer was reduced to 0.1mg/cm 2. The spraying temperatures were all 80 ℃. (platinum loadings of both catalysts in the cathode catalytic layer remain evenly distributed)
Using the polarization curve and power density measured in this example, the double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 5.8% under cathode full humidification. The water retention effect of the catalytic layer is obviously improved under the condition of no humidification of the cathode due to the reduction of the thickness of the catalytic layer caused by the reduction of the platinum loading of the catalytic layer of the cathode, and the maximum power density of the fuel cell is increased by 20% by the double-catalytic-layer cathode in the embodiment.
Example 9
Unlike example 1, in this example, the Pt loading as the anode catalytic layer was 0.1mg/cm 2, and the Pt loading as the cathode catalytic layer was increased to 0.3mg/cm 2. The spraying temperatures were all 80 ℃. (platinum loadings of both catalysts in the cathode catalytic layer remain evenly distributed)
Using the polarization curve and power density measured in this example, the dual catalytic layer cathode in this example increased the maximum power density of the fuel cell by 15.2% under cathode full humidification conditions, due to the increased platinum loading of the catalytic layer. The increase in thickness of the catalytic layer results in a decrease in water retention effect under the cathode non-humidified condition, and the double catalytic layer cathode in this embodiment increases the maximum power density of the fuel cell by 13.6%.
Example 10
Unlike example 1, in this example, the spray coating temperature was reduced to 70 ℃.
Using the polarization curve and power density measured in this example, the double catalytic layer cathode increased the maximum power density of the fuel cell by 11.1% under cathode full humidification. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 19.8% without humidification of the cathode.
Example 11
Unlike example 1, in this example, the spray coating temperature was elevated to 90 ℃.
Using the polarization curve and power density measured in this example, the double catalytic layer cathode increased the maximum power density of the fuel cell by 12.5% under cathode full humidification. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 20% without humidification of the cathode.
Example 12
Unlike example 1, in this example, the black powder obtained by rotary evaporation was heated to 500 ℃ in a mixture of 95% vol argon+5% vol hydrogen and calcined at high temperature for 6 hours.
Using the polarization curve and power density measured in this example, the double catalytic layer cathode increased the maximum power density of the fuel cell by 4.7% under cathode full humidification. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 9.6% without humidification of the cathode.
Example 13
Unlike example 1, in this example, the black powder obtained by rotary evaporation was heated to 700 ℃ in a mixture of 95% vol argon+5% vol hydrogen and calcined at high temperature for 6 hours.
Using the polarization curve and power density measured in this example, the double catalytic layer cathode increased the maximum power density of the fuel cell by 7% under cathode full humidification. The double catalytic layer cathode in this example increased the maximum power density of the fuel cell by 12.3% without humidification of the cathode.
Comparative example 1
A fuel cell prepared by the method of:
And mixing the Pt/C catalyst (40%Pt,Johnson Matthey) with Nafion solution (Dupon), deionized water and isopropanol, and performing ultrasonic treatment to prepare the platinum-carbon catalyst ink. Wherein the concentration of the anode catalyst ink is 10 mg/mL, nafion accounts for 25wt% of the total solid mass, and the volume ratio of water to isopropanol is 1:4. The concentration of the cathode catalyst ink was 10 mg/mL, nafion was 20wt% of the total solids mass, and the volume ratio of water to isopropanol was 1:4.
Pt/C catalyst ink was sprayed on both sides of Gore film (12 μm, gore) as anode and cathode respectively. Wherein the Pt loading in the anode catalytic layer is 0.1mg/cm 2, and the Pt loading in the cathode catalytic layer is 0.2mg/cm 2. The spraying temperatures were all 80 ℃.
After the catalytic layer is sprayed, carbon paper film forming electrodes are added to the anode and cathode, and then the fuel cell is assembled for testing. The test conditions are that the hydrogen flow rate is 300 mL/min, the air flow rate is 1500 mL/min, the back pressure is 100kPa, the test temperature is 80 ℃, the anode is 100% RH, and the two operation conditions of the cathode are respectively 0% RH and 100% RH. The test results are shown in FIG. 3.
Comparative example 2
A fuel cell was different from example 1 in that Nafion in this comparative example accounted for 20wt% of the platinum cobalt alloy catalyst solid mass.
And spraying Pt/C catalyst ink on one side of a Gore membrane (12 mu m, gore) to serve as an anode, preferentially coating platinum-cobalt alloy catalyst ink with acetylene black as a carbon carrier on the other side close to the membrane side, and then spraying platinum-cobalt alloy catalyst ink with Ketjen black 600JD as the carbon carrier to serve as a cathode. Such a catalytic layer is named PtCo/AB-PtCo/KB-600JD.
Fig. 7 (a) is a graph showing the measured polarization curve and power density curve, and the maximum power density of the double catalytic layer cathode in this example was reduced by 11.8% under the cathode full humidification condition, compared to the cathode catalytic layer in example 1. Fig. 7 (b) is a polarization curve and a power density curve measured under the cathode non-humidified condition, and the maximum power density of the double cathode catalysis in this example is reduced by 22.4%. This example demonstrates that the increasing gradient of pores of the dual catalytic layer from the proton exchange membrane to the gas diffusion layer facilitates the improvement of peak power density, while the use of a high specific surface area catalytic layer near the membrane side facilitates the maintenance of fuel cell performance without humidification.
FIG. 7 (c) is an electrochemical impedance spectrum at 2A/cm 2 at 100% RH, which shows that a lower mass transfer resistance is obtained when the catalytic layer has a gradient characteristic of gradually increasing pores from the proton exchange membrane to the gas diffusion layer. In contrast, when the pores of the catalytic layer gradually decrease from the proton exchange membrane to the gas diffusion layer pores, a significant mass transfer resistance occurs. The same phenomenon can be observed under the condition of no humidification in FIG. 7 (d), and the high-frequency resistance of the PtCo/AB-PtCo/KB-600JD catalytic layer is also obviously increased under the condition of no humidification, which shows the water-retaining capacity of the catalytic layer with high specific surface area close to the proton exchange membrane side.
Comparative example 3
Unlike example 1, in this comparative example, nafion represents 20wt% of the solid mass of the platinum cobalt alloy catalyst.
One side of a Gore film (12 μm, gore) was sprayed with Pt/C catalyst ink as an anode, and the other side was sprayed with mixed platinum cobalt alloy catalyst ink using acetylene black and ketjen black 600JD as carbon carriers as a cathode.
Fig. 8 (a) is a graph of measured polarization and power density, and the maximum power density of the double catalytic layer cathode in this example was reduced by 13.2% under the cathode full humidification condition, compared to the cathode catalytic layer of example 1. Fig. 8 (b) is a polarization curve and a power density curve measured under the cathode non-humidified condition, and the maximum power density of the double cathode catalysis in this example is reduced by 28.9%. This example illustrates that the hybrid dual catalytic layer structure has no optimal effect on the improvement of fuel cell performance.
TABLE 1
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (8)
1.A fuel cell double catalytic layer cathode, characterized by comprising a first catalytic layer arranged on one side of a proton exchange membrane and a second catalytic layer arranged on one side of a gas diffusion layer;
The first catalytic layer and the second catalytic layer are respectively and independently platinum-cobalt alloy catalytic layers based on carbon carriers, the specific surface area of the first catalytic layer is 500-900 m 2/g, the secondary pore size is 20-50 nm, the specific surface area of the second catalytic layer is 50-150 m 2/g, and the secondary pore size is 70-100 nm;
The carbon carrier comprises acetylene black, ketjen black or conductive carbon black;
And the Pt carrying capacity in the cathode is 0.1-0.3 mg/cm 2.
2. The method for preparing a double catalytic layer cathode for a fuel cell according to claim 1, comprising the steps of:
Uniformly mixing a carbon carrier, water, a platinum source and a cobalt source to obtain a platinum-cobalt precursor aqueous solution;
transferring the platinum cobalt precursor aqueous solution into rotary steaming equipment for steaming and drying treatment;
Roasting the powder obtained by evaporation in inert atmosphere, and carrying out acid washing and drying to obtain a platinum-cobalt alloy catalyst based on a carbon carrier;
Uniformly mixing the platinum-cobalt alloy catalyst based on the carbon carrier, water, an organic solvent and an ionomer solution to obtain a first catalytic layer ink and a second catalytic layer ink respectively;
And spraying the first catalytic layer ink and the second catalytic layer ink on the proton exchange membrane in sequence to obtain the fuel cell double-catalytic-layer cathode.
3. The method for preparing the fuel cell double-catalytic-layer cathode according to claim 2, wherein the mixing of the carbon carrier, the water, the platinum source and the cobalt source is performed under a sealed condition, the stirring speed is 300-500 rpm, the stirring temperature is 25-35 ℃, the stirring time is 12-36 h, and the concentration of the platinum-cobalt precursor aqueous solution is 3-3.5 g/L.
4. The method for preparing a double catalytic layer cathode for a fuel cell according to claim 2, wherein the rotation speed of the rotary evaporation device is 100-150 rpm, the evaporation temperature is 50-60 ℃, and the vacuum condition is one atmosphere.
5. The method for preparing the fuel cell double-catalytic-layer cathode according to claim 2, wherein the roasting temperature is 500-800 ℃, the roasting time is 2-6 h, and the acid washing is sequentially carried out by adopting 0.5-1M acid solution and water.
6. The method for preparing a double catalytic layer cathode for a fuel cell according to claim 2, wherein when the platinum-cobalt alloy catalyst based on a carbon carrier, water, an organic solvent and an ionomer solution are mixed, the concentration of the mixed solution is 4-8 mg/mL, the mixing mode is ultrasonic dispersion, and the ionomer content accounts for 10-30 wt% of the total mass of the solid material.
7. The method for preparing a fuel cell double catalytic layer cathode according to any one of claims 2 to 6, wherein the spraying temperature is 70 to 90 ℃.
8. A fuel cell comprising the fuel cell double-catalytic-layer cathode according to claim 1, or a fuel cell double-catalytic-layer cathode produced by the production method of the fuel cell double-catalytic-layer cathode according to any one of claims 2 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411281684.7A CN118800919B (en) | 2024-09-13 | 2024-09-13 | Fuel cell double catalytic layer cathode, preparation method and fuel cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411281684.7A CN118800919B (en) | 2024-09-13 | 2024-09-13 | Fuel cell double catalytic layer cathode, preparation method and fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118800919A CN118800919A (en) | 2024-10-18 |
| CN118800919B true CN118800919B (en) | 2025-02-11 |
Family
ID=93030318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411281684.7A Active CN118800919B (en) | 2024-09-13 | 2024-09-13 | Fuel cell double catalytic layer cathode, preparation method and fuel cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118800919B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102104155A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Low-platinum cathode catalyst layer used for fuel cell and application thereof |
| CN113113623A (en) * | 2021-03-26 | 2021-07-13 | 中国科学技术大学 | Synthesis method of carbon-supported platinum-based intermetallic compound nano material and electrocatalysis application thereof |
| CN116722156A (en) * | 2023-06-13 | 2023-09-08 | 上海空间电源研究所 | A high-temperature proton exchange membrane fuel cell cathode and preparation method, membrane electrode |
| CN116799233A (en) * | 2022-03-15 | 2023-09-22 | 中自环保科技股份有限公司 | Composite catalytic layer, catalytic membrane electrode, fuel cell and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114204046A (en) * | 2021-10-28 | 2022-03-18 | 中国汽车技术研究中心有限公司 | Biomass-based in-situ reduction noble metal-based fuel cell catalyst |
| CN116387530A (en) * | 2023-03-01 | 2023-07-04 | 上海空间电源研究所 | Fuel cell gradient hole distribution double-catalytic-layer cathode and preparation method thereof |
-
2024
- 2024-09-13 CN CN202411281684.7A patent/CN118800919B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102104155A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Low-platinum cathode catalyst layer used for fuel cell and application thereof |
| CN113113623A (en) * | 2021-03-26 | 2021-07-13 | 中国科学技术大学 | Synthesis method of carbon-supported platinum-based intermetallic compound nano material and electrocatalysis application thereof |
| CN116799233A (en) * | 2022-03-15 | 2023-09-22 | 中自环保科技股份有限公司 | Composite catalytic layer, catalytic membrane electrode, fuel cell and application |
| CN116722156A (en) * | 2023-06-13 | 2023-09-08 | 上海空间电源研究所 | A high-temperature proton exchange membrane fuel cell cathode and preparation method, membrane electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118800919A (en) | 2024-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3053648B1 (en) | Use of carbon powder in fuel cell catalyst, fuel cell catalyst with carbon powder, electrode catalyst layer, membrane electrode assembly, and fuel cell | |
| JP6603396B2 (en) | Carbon powder for fuel cell and catalyst, electrode catalyst layer, membrane electrode assembly and fuel cell using carbon powder for fuel cell | |
| CN102306810A (en) | Composite catalyst of self-humidifying fuel cell and manufacturing method and application thereof | |
| JP2004363056A (en) | Catalyst carrying electrode for polymer electrolyte fuel cell and its manufacturing method | |
| CN115036522A (en) | Method for preparing alloy catalyst for fuel cell in limited area | |
| CN101140991B (en) | A proton exchange membrane fuel cell electrode catalyst layer and its preparation | |
| WO2024088284A1 (en) | Membrane electrode assembly for fuel cell and application thereof | |
| CN106058276A (en) | Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode | |
| WO2016152506A1 (en) | Carbon powder for fuel cell, catalyst using said carbon powder for fuel cell, electrode catalyst layer, membrane electrode assembly, and fuel cell | |
| CN110931815A (en) | Preparation method of fuel cell carbon-supported platinum-based catalyst | |
| CN101337183A (en) | Preparation method of direct alcohol fuel cell cathode catalyst | |
| CN118800919B (en) | Fuel cell double catalytic layer cathode, preparation method and fuel cell | |
| CN118384905A (en) | ZIF-derived porous nitrogen-containing carbon-based carrier with high specific surface area and preparation method and application thereof | |
| CN117525462A (en) | Solvent-free preparation method and application of carbon-supported platinum-based alloy catalyst | |
| CN114899418B (en) | Platinum catalyst and preparation method and application thereof | |
| JP7346729B2 (en) | Fuel cell catalyst, method for producing the same, and membrane-electrode assembly including the same | |
| CN108417849A (en) | Preparation of a carbon material catalyst based on ferrite@chitosan Schiff base | |
| CN116314890B (en) | A Pt-Fe alloy catalyst and its preparation method and application in proton exchange membrane fuel cells | |
| EP4421922A1 (en) | Fuel cell catalyst, method for manufacturing same, and fuel cell comprising same | |
| CN114408893B (en) | Pore structure control method and application of a porous carbon material | |
| CN115285972B (en) | A kind of porous carbon supported metal type nanomaterial and its preparation method | |
| CN116332180A (en) | Iridium-supported Molybdenum Carbide Nano Curds and Their Preparation and Application in Hydrogen Oxidation | |
| CN119050378A (en) | Variable contact angle non-noble metal base membrane electrode and preparation method and application thereof | |
| JP2025045934A (en) | Electrode catalyst and fuel cell system | |
| CN117317266A (en) | Preparation method and application of mesoporous carbon supported platinum single-atom or cluster catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |