CN115064710B - Membrane electrode CCM, preparation method thereof, membrane electrode assembly MEA and fuel cell - Google Patents
Membrane electrode CCM, preparation method thereof, membrane electrode assembly MEA and fuel cell Download PDFInfo
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- 239000003054 catalyst Substances 0.000 claims abstract description 340
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- 238000005507 spraying Methods 0.000 claims description 57
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
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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]
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The application relates to a membrane electrode CCM and a preparation method thereof, and a membrane electrode assembly MEA and a fuel cell. The technical scheme mainly adopted is as follows: the membrane electrode CCM comprises a proton exchange membrane and a cathode catalyst layer coated on the proton exchange membrane; wherein the cathode catalyst layer comprises a first cathode catalyst layer and a second cathode catalyst layer; wherein the first cathode catalyst layer is coated on the proton exchange membrane; wherein the first cathode catalyst in the first cathode catalyst layer is a catalyst with a three-dimensional network structure; a second cathode catalyst layer is sprayed on the first cathode catalyst layer; wherein the second cathode catalyst in the second cathode catalyst layer is a granular catalyst. The application is mainly used for the cathode catalyst layer of the membrane electrode CCM and has the advantages of high mass transfer efficiency, good durability, low load and less surface defects, so as to improve the performances of the membrane electrode CCM, the membrane electrode assembly MEA and the fuel cell.
Description
Technical Field
The application relates to the technical field of fuel cells, in particular to a membrane electrode CCM and a preparation method thereof, a membrane electrode assembly MEA and a fuel cell.
Background
The world is faced with an increasing reduction, even exhaustion, of fossil energy sources and high requirements of human beings on environment protection, and an environment-friendly energy source is urgently needed. The fuel cell should be transported into our line of sight. Fuel cells are one of the most great applications in human history in which hydrogen and oxygen produce electric energy through chemical reactions, and the effluent of fuel cells is water. Therefore, the fuel cell becomes a research hot spot in the fields of energy science and electrochemistry, and meanwhile, the fuel cell has the characteristics of low operation temperature, high energy efficiency, renewable fuel and the like.
In a fuel cell, the preparation technology of the membrane electrode CCM is one of the most core technologies of the fuel cell, and meanwhile, the preparation technology of the membrane electrode CCM is also one of the most difficult breakthrough technologies in the study of the proton exchange membrane fuel cell.
The inventors of the present application studied and found that: the cathode catalytic layer on the membrane electrode CCM of the fuel cell at the present stage is of a single shape, and has obvious advantages and disadvantages, such as: the cathode catalytic layer prepared by adopting the spraying process has the advantages of few surface defects, serious influence on mass transfer efficiency by the thickness of the catalytic layer, low preparation efficiency, incomplete utilization of a reaction interface, low utilization rate of slurry and the like; for example: the cathode catalytic layer prepared by the coating process has the advantages of higher mass transfer efficiency, high preparation efficiency, high reaction interface utilization rate, higher slurry utilization rate, serious defect on the surface of the catalytic layer, easy falling of the catalytic layer and influence on durability.
Disclosure of Invention
In view of the above, the present application provides a membrane electrode CCM, a method for preparing the same, a membrane electrode assembly MEA, and a fuel cell, and aims to solve the problems of large surface defects, mass transfer affected by a catalyst layer thickness, low interface utilization, and poor durability of a cathode catalyst layer of an existing membrane electrode CCM, so as to improve performances of the membrane electrode CCM, the membrane electrode assembly MEA, and the fuel cell.
In order to achieve the above purpose, the present application mainly provides the following technical solutions:
in one aspect, embodiments of the present application provide a membrane electrode CCM for use in a fuel cell, wherein the membrane electrode CCM comprises a proton exchange membrane and a cathode catalyst layer coated on the proton exchange membrane; wherein the cathode catalyst layer comprises:
a first cathode catalyst layer coated on the proton exchange membrane; wherein the first cathode catalyst in the first cathode catalyst layer is a catalyst with a three-dimensional network structure;
a second cathode catalyst layer sprayed on the first cathode catalyst layer; wherein the second cathode catalyst in the second cathode catalyst layer is a granular catalyst.
Preferably, the first cathode catalyst is a composite carbon carrier supported alloy catalyst; wherein, in the composite carbon carrier supported alloy catalyst: the composite carbon carrier is a composite material comprising a granular carbon material and a linear carbon material; the alloy is platinum-cobalt alloy; preferably, the platinum-cobalt alloy contains 10-60wt%, preferably 15-50wt% of platinum; preferably, the content of the platinum-cobalt alloy is 20-60wt%; preferably, the granular carbon material is one or more of mesoporous carbon, carbon microspheres and amorphous carbon; preferably, the linear carbon material is carbon nanotubes and/or carbon fibers.
Preferably, the second cathode catalyst is a semi-graphitized pure platinum catalyst; preferably, the second cathode catalyst is a semi-graphitized pure platinum catalyst of TEC10EA50E type.
Preferably, the first cathode catalyst layer has a loading of0.1-0.2mg/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the And/or the second cathode catalyst layer has a loading of 0.1 to 0.2mg/cm 2 。
Preferably, the membrane electrode CCM further comprises an anode catalyst layer sprayed on the proton exchange membrane; wherein, the anode catalyst in the anode catalyst layer is a granular catalyst; preferably, the anode catalyst is a semi-graphitized pure platinum catalyst, and further a semi-graphitized pure platinum catalyst of TEC10EA50E type is selected; further preferably, the anode catalyst layer has a loading of 0.1 to 0.2mg/cm 2 。
On the other hand, the embodiment of the application provides a preparation method of a membrane electrode CCM, wherein the preparation method of the membrane electrode CCM comprises the following steps:
preparing a first cathode catalyst layer: coating a first catalyst slurry on a first surface of a proton exchange membrane by adopting a coating process to form a first cathode catalyst layer;
preparing a second cathode catalyst layer: spraying a second catalyst slurry on the first cathode catalyst layer by adopting a spraying process to form a second cathode catalyst layer;
preferably, the first catalyst slurry comprises a first cathode catalyst and a solvent; wherein the solid content of the first catalyst slurry is 6-10wt%; the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol; further preferably, the mass ratio of the perfluorosulfonic acid solution, the PTFE emulsion, the deionized water and the alcohol is (1.5-2): (0.5-1): (3-5): (6-8);
preferably, the second catalyst slurry comprises a second cathode catalyst and a solvent; wherein the solid content of the second catalyst slurry is 6-10wt%; the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol; further preferably, the mass ratio of the perfluorosulfonic acid solution, the PTFE emulsion, the deionized water and the alcohol is (1.5-2): (0.5-1): (3-5): (6-8).
Preferably, the step of preparing the first cathode catalyst layer includes:
the first catalyst sizing agent is added into preheated coating equipment after being subjected to ultrasonic dispersion; then, preparing a first cathode catalyst layer on a first face of the proton exchange membrane by using a coating device;
preferably, the time for ultrasonic dispersion of the first catalyst slurry is 15-30min;
preferably, the coating equipment is sheet type coating equipment or roll-to-roll coating equipment;
preferably, the loading is set to 0.1-0.2mg/cm when the first cathode catalyst layer is prepared on the first side of the proton exchange membrane using a coating apparatus 2 ；
Preferably, before the step of preparing the first cathode catalyst layer, it includes: cleaning and preheating coating equipment; further preferably, the step of cleaning and preheating includes: and (3) cleaning the coating equipment by adopting ethanol, starting up for temperature debugging, setting the preheating temperature to be higher than 70 ℃, and finishing preheating after the temperature is stable.
Preferably, the step of preparing the second cathode catalyst layer includes:
the second catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; then, preparing a second cathode catalyst layer on the first cathode catalyst layer by adopting spraying equipment;
preferably, the second catalyst slurry is subjected to ultrasonic dispersion for 15-30min;
preferably, the spraying equipment is ultrasonic spraying equipment;
preferably, the loading is set to 0.1-0.2mg/cm when preparing the second cathode catalyst layer on the first cathode catalyst layer using a spray apparatus 2 ；
Preferably, before the step of preparing the second cathode catalyst layer, it includes: cleaning and preheating the spraying equipment; further preferably, the step of cleaning and preheating includes: and cleaning the spraying equipment by adopting ethanol, starting up for temperature adjustment, setting the preheating temperature to be higher than 70 ℃, and finishing preheating after the temperature is stable.
Preferably, the preparation method of the membrane electrode CCM further comprises:
preparing an anode catalyst layer: preparing an anode catalyst layer on the second surface of the proton exchange membrane by using a spraying device, wherein the loading is preferably set to be 0.1-0.2mg/cm 2 ；
Preferably, after the preparation of the first cathode catalyst layer, the second cathode catalyst layer and the anode catalyst layer is completed, drying treatment is performed to obtain a membrane electrode CCM; further preferably, the temperature of the drying treatment is greater than 70 ℃.
In yet another aspect, an embodiment of the present application provides a membrane electrode assembly MEA, where the membrane electrode assembly MEA includes a membrane electrode CCM as described in any one of the above.
In yet another aspect, an embodiment of the present application provides a fuel cell, where the fuel cell includes the membrane electrode CCM according to any one of the above or the membrane electrode assembly MEA according to the above.
Compared with the prior art, the membrane electrode CCM and the preparation method thereof, and the membrane electrode assembly and the fuel cell have at least the following beneficial effects:
in one aspect, an embodiment of the present application provides a membrane electrode CCM and a method for preparing the same, where the membrane electrode CCM includes a proton exchange membrane and a cathode catalyst layer coated on the proton exchange membrane; wherein the cathode catalyst layer comprises a first cathode catalyst layer and a second cathode catalyst layer; wherein the first cathode catalyst layer is coated on the proton exchange membrane; wherein, the first cathode catalyst in the first cathode catalyst layer is a catalyst with a three-dimensional network structure. The second cathode catalyst layer is sprayed on the first cathode catalyst layer; wherein the second cathode catalyst in the second cathode catalyst layer is a granular catalyst. By the above arrangement: (1) The catalyst in the inner layer (first cathode catalyst layer) of the cathode catalyst layer is a catalyst with a three-dimensional network structure, so that the contact between an active substance and a current collector as well as between the active substance and a proton membrane can be enhanced, a three-phase reaction area is increased, more reaction space is provided, the utilization rate of platinum is greatly improved, and the mass transfer efficiency and the power generation efficiency of the fuel cell are improved; (2) The inner layer of the cathode catalyst layer (the first cathode catalyst layer) is set as a coating layer, and the coating process is selected according to the three-dimensional network structure characteristics of the first cathode catalyst, so that the preparation efficiency can be greatly improved, and the mass production is realized; (3) The catalyst in the inner layer of the cathode catalyst layer is a catalyst with a three-dimensional network structure, so that the mechanical strength of the catalyst layer is greatly enhanced; meanwhile, the outer layer (the second cathode catalyst layer) of the cathode catalyst layer is a spray coating layer, so that the surface compactness of the cathode catalyst layer can be improved, the surface defects are reduced, and meanwhile, the semi-graphitized carrier has a certain improvement on the durability, therefore, the two layers of cathode catalyst layers of the embodiment of the application can well avoid the corrosion of the carbon carrier in the cathode catalyst layer caused by current, and the durability is greatly improved; (4) Although the outer layer of the cathode catalyst layer (second cathode catalyst layer) is a spray coating layer, the second cathode catalyst layer can be made thin due to the existence of the first cathode catalyst layer, so that the cathode catalyst layer is not affected by the thickness. In summary, the synergistic effect of the first cathode catalyst layer and the second cathode catalyst layer makes the cathode catalyst layer of the membrane electrode CCM have the characteristics of high mass transfer efficiency, good durability, low load and few surface defects.
On the other hand, the embodiments of the present application provide a membrane electrode assembly MEA and a fuel cell, which include the membrane electrode CCM described above, so that the membrane electrode assembly MEA and the fuel cell have the beneficial effects described in any of the foregoing, and are not described in detail herein.
In summary, the membrane electrode CCM, the preparation method thereof, the membrane electrode assembly and the fuel cell provided by the embodiment of the application solve the problems of mass transfer, low slurry utilization rate, low interface utilization rate, poor durability and the like caused by the surface defect of the cathode catalytic layer of the membrane electrode CCM and the thickness of the catalytic layer, thereby improving the performances of the membrane electrode CCM, the membrane electrode assembly MEA and the fuel cell.
The foregoing description is only an overview of the present application, and is intended to provide a better understanding of the present application, as it is embodied in the following description, with reference to the preferred embodiments of the present application and the accompanying drawings.
Drawings
Fig. 1 is a schematic structural diagram of a membrane electrode CCM according to an embodiment of the present application;
FIG. 2 is a scanning electron microscope image of the membrane electrode CCM prepared in example 1; wherein, fig. 2A is a cross-sectional scanning electron microscope image of the membrane electrode CCM prepared in example 1; FIG. 2B is a surface scanning electron microscope image of the cathode catalyst layer of the membrane electrode CCM prepared in example 1;
FIG. 3 is a cross-sectional Scanning Electron Microscope (SEM) of the membrane electrode CCM prepared in example 2;
FIG. 4 is a scanning electron microscope image of the membrane electrode CCM prepared in comparative example 1; wherein, fig. 4A is a cross-sectional scanning electron microscope image of the membrane electrode CCM prepared in the comparative example; fig. 4B is a surface scanning electron microscope image of the cathode catalyst layer of the membrane electrode CCM prepared in the comparative example;
FIG. 5 is a graph showing the performance of the membrane electrode CCM prepared in example 1 and comparative example 1;
fig. 6 is a graph showing the performance of the membrane electrode CCM prepared in example 2 and comparative example 1.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the application, the following detailed description refers to the specific implementation, structure, characteristics and effects according to the application of the application with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
In one aspect, an embodiment of the present application provides a membrane electrode CCM, as shown in fig. 1, where the membrane electrode CCM includes a proton exchange membrane 1 and a cathode catalyst layer coated on the proton exchange membrane 1; wherein the cathode catalyst layer includes a first cathode catalyst layer 21 and a second cathode catalyst layer 22; wherein the first cathode catalyst layer 21 is coated on the proton exchange membrane 1; wherein the first cathode catalyst in the first cathode catalyst layer 21 is a catalyst having a three-dimensional network structure. The second cathode catalyst layer 22 is sprayed on the first cathode catalyst layer 21; wherein the second cathode catalyst in the second cathode catalyst layer 22 is a particulate catalyst.
Regarding the design of the membrane electrode CCM, it should be noted here that: (1) The catalyst in the inner layer (first cathode catalyst layer) of the cathode catalyst layer is a catalyst with a three-dimensional network structure, so that a three-phase reaction area can be increased to provide more reaction space, and the mass transfer efficiency and the power generation efficiency of the fuel cell are improved. (2) The inner layer of the cathode catalyst layer (the first cathode catalyst layer) is taken as a coating layer, and a coating process is selected according to the structure of the first cathode catalyst, so that the preparation efficiency can be greatly improved, and the mass production can be realized; (3) The catalyst in the inner layer of the cathode catalyst layer is a catalyst with a three-dimensional network structure, so that the inner layer has excellent mechanical properties, and meanwhile, the outer layer (the second cathode catalyst layer) of the cathode catalyst layer is a spray coating layer, so that the surface compactness of the cathode catalyst layer can be improved, the surface defects can be reduced, the corrosion of a carbon carrier in the cathode catalyst layer caused by current can be well avoided, and the durability can be greatly improved; (4) Although the outer layer of the cathode catalyst layer (second cathode catalyst layer) is a spray coating layer, the second cathode catalyst layer can be made thin due to the existence of the first cathode catalyst layer, so that the cathode catalyst layer is not affected by the thickness. In summary, the synergistic effect of the first cathode catalyst layer and the second cathode catalyst layer makes the cathode catalyst layer of the membrane electrode CCM have the characteristics of high mass transfer efficiency, good durability, low load and few surface defects.
Preferably, the first cathode catalyst is a composite carbon support alloy supported catalyst (composite carbon support alloy catalyst); wherein, the composite carbon carrier in the composite carbon carrier supported alloy catalyst is a composite carrier material composed of a granular carbon material and a linear carbon material; the alloy in the composite carbon carrier supported alloy catalyst is platinum-cobalt alloy; preferably, the alloy content in the composite carbon carrier supported alloy catalyst is 20-60wt%; preferably, the granular carbon material is one or more of mesoporous carbon, carbon microsphere and amorphous carbon; preferably, the linear carbon material is carbon nanotubes and/or carbon fibers; preferably, the first cathode catalyst layer has a loading of 0.1 to 0.2mg/cm 2 . As can be seen in the view of figure 1,the first cathode catalyst layer 21 has a particulate carbon support and a linear carbon support therein, and forms a three-dimensional composite network structure. The three-phase composite network structure can enhance the contact between the active substance and the current collector and the proton membrane, thereby forming more three-phase reaction interfaces and being beneficial to improving the utilization rate of platinum. In addition, the three-dimensional composite network structure greatly enhances the mechanical strength of the catalytic layer (for the composite carbon support supported alloy catalyst mentioned in the application, the prior art of the inventor of the application is specifically referred to as patent application number 202110674380.7).
Preferably, the second cathode catalyst is a semi-graphitized pure platinum catalyst; preferably, a semi-graphitized pure platinum catalyst of TEC10EA50E type is selected; preferably, the second cathode catalyst layer has a loading of 0.1 to 0.2mg/cm 2 . The second cathode catalyst layer adopts a semi-graphitized pure platinum catalyst, so that crack defects and the like on the surface of the cathode catalyst layer are reduced, and meanwhile, the durability of the semi-graphitized carrier is improved to a certain extent.
Preferably, as shown in fig. 1, the membrane electrode CCM further comprises an anode catalyst layer 3 sprayed on the proton exchange membrane 1; wherein, the anode catalyst in the anode catalyst layer 3 is a granular catalyst. Preferably, the anode catalyst is a semi-graphitized pure platinum catalyst, and further a semi-graphitized pure platinum catalyst of TEC10EA50E type is selected; preferably, the anode catalyst layer has a loading of 0.1 to 0.2mg/cm 2 . What should be stated here is: for fuel cells, the exchange current density of the anode is several orders of magnitude that of the cathode, so that the anode catalyst layer requires only an extremely small amount of platinum to meet the requirements (so that the anode catalyst layer requires only one layer).
On the other hand, the embodiment of the application provides a preparation method of the membrane electrode CCM, which comprises the following steps:
preparing a catalyst slurry:
preparing a first catalyst slurry: weighing a composite carbon carrier supported alloy catalyst, then mixing with a solvent, dispersing to prepare a first catalyst slurry, and keeping the slurry at a low temperature for later use; wherein the solvent consists of a perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol (wherein the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the alcohol is (1.5-2): 0.5-1): 3-5): 6-8).
Preparing a second catalyst slurry: weighing a semi-graphitized pure platinum catalyst, mixing with a solvent, dispersing to prepare second catalyst slurry, and keeping at a low temperature for later use; wherein the solvent consists of a perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol (wherein the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the alcohol is (1.5-2): 0.5-1): 3-5): 6-8).
Cleaning and preheating: the coating equipment and the spraying equipment used are cleaned and preheated. Wherein, the cleaning treatment comprises: ethanol is used for cleaning the pipeline and main parts; preheating: and starting up to perform temperature action debugging, wherein the temperature is higher than 70 ℃, and after the temperature is stable, preheating is completed.
Preparing a first cathode catalyst layer: after ultrasonic dispersion (ultrasonic dispersion for 15min-30 min), the first catalyst slurry is added into preheated coating equipment, and then coated on a proton exchange membrane to prepare a first cathode catalyst layer, wherein the loading is set to be 0.1-0.2mg/cm 2 。
Preparing a second cathode catalyst layer: adding the mixture into preheated spraying equipment (ultrasonic dispersion for 15-30 min), preparing a second cathode catalyst layer on the first cathode catalyst layer by using spraying equipment, and setting the loading to 0.1-0.2mg/cm 2 。
Preparing an anode catalyst layer: after the cathode catalyst layer is prepared, turning over on spraying equipment, starting to prepare the anode catalyst layer, wherein the loading is set to be 0.1-0.2mg/cm 2 。
And (3) drying: and after the preparation of the first cathode catalyst layer, the second cathode catalyst layer and the anode catalyst layer is finished, drying treatment is carried out to obtain the membrane electrode CCM.
The application is further illustrated below by means of specific experimental examples:
example 1
The preparation method of the membrane electrode CCM of the fuel cell comprises the following specific preparation steps:
1) Weighing the composite carbon carrier supported alloy catalyst, preparing a first catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (6 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1.5:0.5:3:6.
wherein, in the composite carbon carrier supported alloy catalyst selected in the step: the loading was 50% (i.e., the alloy content in the composite carbon supported catalyst was 50%), wherein the composite carbon supported alloy catalyst was prepared as described in example 1 of our earlier patent application 202110674380.7.
2) Weighing a semi-graphitized pure platinum catalyst of TEC10EA50E type, preparing a second catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (6 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1.5:0.5:3:6.
3) Cleaning and preheating coating equipment and spraying equipment used for preparing the catalytic layer; wherein, the cleaning treatment comprises: ethanol is used for cleaning the pipeline and main parts; preheating: and starting up to perform temperature action debugging, wherein the temperature is higher than 70 ℃, and preheating is completed after the temperature is stable.
The prepared first catalyst slurry is added into preheated coating equipment after being subjected to ultrasonic dispersion; wherein, after 15min of ultrasonic dispersion time, the mixture is added into a material storage mechanism of a coating machine.
The prepared second catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; wherein, the ultrasonic dispersion time is 15min, and then the ultrasonic dispersion time is added into a storage mechanism of the spraying machine.
4) Beginning preparation of a first cathode catalyst layer on a proton exchange membrane with a first catalyst slurry in a coating apparatus, the loading was set at 0.2mg/cm 2 The number of coating times was 1.
5) By spraying apparatusStarting to prepare a second cathode catalyst layer on the first cathode catalyst layer, the loading being set at 0.1mg/cm 2 The spraying times are 1 time.
6) Turning over the prepared cathode catalytic layer on spraying equipment, and starting to prepare the anode catalytic layer. Preparing an anode catalyst layer on the proton exchange membrane with a second catalyst slurry in a spraying device; wherein the loading was set at 0.1mg/cm 2 Spraying times are 1 time;
7) And drying and taking down the CCM, and finishing the preparation, wherein the drying temperature is higher than 70 ℃.
FIG. 2A is a cross-sectional Scanning Electron Microscope (SEM) of a membrane electrode CCM prepared in example 1; FIG. 2B is a surface scanning electron microscope image of the cathode catalyst layer of the membrane electrode CCM prepared in example 1; as can be seen from fig. 2A and 2B: the first cathode catalyst layer is provided with granular and linear carbon materials, and a three-dimensional composite network structure is formed, and the three-dimensional composite network structure can enhance the contact between active substances, a current collector and a proton membrane, so that more three-phase reaction interfaces are formed, and the utilization rate of platinum is improved; the second cathode catalyst layer is made of granular carbon material, so that the defect problem on the surface of the catalyst layer is effectively solved.
Example 2
The preparation method of the membrane electrode CCM of the fuel cell comprises the following specific preparation steps:
1) Weighing the composite carbon carrier supported alloy catalyst, preparing a first catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (4 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1.5:1:3:6.
wherein, in the composite carbon carrier supported alloy catalyst selected in the step: the loading was 50%, wherein the composite carbon support supported alloy catalyst was prepared as described in example 1 of our earlier patent application 202110674380.7.
2) Weighing a semi-graphitized pure platinum catalyst of TEC10EA50E type, preparing a second catalyst slurry (solid content is 7%) with a solvent, and preserving at a low temperature (4 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1:1:4:6.
3) Cleaning and preheating coating equipment and spraying equipment used for preparing the catalytic layer; wherein, the cleaning treatment comprises: ethanol is used for cleaning the pipeline and main parts; preheating: and starting up to perform temperature action debugging, wherein the temperature is higher than 70 ℃, and preheating is completed after the temperature is stable.
The prepared first catalyst slurry is added into preheated coating equipment after being subjected to ultrasonic dispersion; wherein, after ultrasonic dispersion time is 30min, the mixture is added into a material storage mechanism of a coating machine.
The prepared second catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; wherein, the ultrasonic dispersion time is 30min, and then the ultrasonic dispersion time is added into a storage mechanism of the spraying machine.
4) Beginning preparation of a first cathode catalyst layer on a proton exchange membrane with a first catalyst slurry in a coating apparatus, the loading was set at 0.1mg/cm 2 The number of coating times was 1.
5) Starting preparation of the second cathode catalyst layer on the first cathode catalyst layer with the second catalyst slurry in the spray equipment, the loading was set to 0.2mg/cm 2 The spraying times are 2 times.
6) Turning over the prepared cathode catalytic layer on spraying equipment, and starting to prepare the anode catalytic layer. Preparing an anode catalyst layer on the proton exchange membrane with a second catalyst slurry in a spraying device; wherein the loading was set at 0.1mg/cm 2 Spraying times are 1 time;
7) And drying and taking down the CCM, and finishing the preparation, wherein the drying temperature is higher than 70 ℃.
FIG. 3 is a scanning electron microscope image of a cross section of a membrane electrode CCM prepared in example 2; as can be seen from fig. 3: the first cathode catalyst layer is provided with granular and linear carbon materials, and a three-dimensional composite network structure is formed, and the three-dimensional composite network structure can enhance the contact between active substances, a current collector and a proton membrane, so that more three-phase reaction interfaces are formed, and the utilization rate of platinum is improved; the second cathode catalyst layer is made of granular carbon material, so that the defect problem on the surface of the catalyst layer is effectively solved.
Comparative example 1
Comparative example 1 a fuel cell membrane electrode CCM was prepared, specifically by the following steps:
1) Weighing a semi-graphitized pure platinum catalyst of TEC10EA50E type, preparing catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (2 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1:1:5:6.
2) Cleaning and preheating spraying equipment used for preparing the catalytic layer; wherein, the cleaning treatment comprises: ethanol is used for cleaning the pipeline and main parts; preheating: and starting up to perform temperature action debugging, wherein the temperature is higher than 70 ℃, and preheating is completed after the temperature is stable.
The prepared catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; wherein, the ultrasonic dispersion time is 30min, and then the ultrasonic dispersion time is added into a storage mechanism of the spraying machine.
3) Preparation of a cathode catalyst layer on a proton exchange membrane with catalyst slurry in a spray apparatus, the loading was set at 0.3mg/cm 2 The spraying times are 3 times.
6) Turning over the prepared cathode catalytic layer on spraying equipment, and starting to prepare the anode catalytic layer. Preparing an anode catalyst layer on the proton exchange membrane by using catalyst slurry in spraying equipment; wherein the loading was set at 0.1mg/cm 2 Spraying times are 1 time;
7) And drying and taking down the CCM, and finishing the preparation, wherein the drying temperature is higher than 70 ℃.
As can be seen from fig. 4A and 4B: the cathode catalytic layer is a catalytic layer without a specific structure, has obvious surface defects, has cracks, has uneven and unstable reaction interface, has poor mass transfer effect, and has obvious defects.
Comparative example 2
Comparative example 2a fuel cell membrane electrode CCM was prepared, differing from example 2 in that: the cathode catalyst layer is only provided with one composite carbon carrier supported alloy catalyst layer; the preparation method comprises the following steps:
1) Weighing the composite carbon carrier supported alloy catalyst, preparing a first catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (4 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1:1:2:6.
wherein, in the composite carbon carrier supported alloy catalyst selected in the step: the loading was 50%, wherein the composite carbon support supported alloy catalyst was prepared as described in example 1 of our earlier patent application 202110674380.7.
2) Weighing a semi-graphitized pure platinum catalyst of TEC10EA50E type, preparing a second catalyst slurry (the solid content is 7 wt%) with a solvent, and preserving at a low temperature (4 ℃) for later use; wherein the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and ethanol; wherein, the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the ethanol is 1:1:2:6.
3) Cleaning and preheating coating equipment and spraying equipment used for preparing the catalytic layer; wherein, the cleaning treatment comprises: ethanol is used for cleaning the pipeline and main parts; preheating: and starting up to perform temperature action debugging, wherein the temperature is higher than 70 ℃, and preheating is completed after the temperature is stable.
The prepared first catalyst slurry is added into preheated coating equipment after being subjected to ultrasonic dispersion; wherein, after ultrasonic dispersion time is 30min, the mixture is added into a material storage mechanism of a coating machine.
The prepared second catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; wherein, the ultrasonic dispersion time is 30min, and then the ultrasonic dispersion time is added into a storage mechanism of the spraying machine.
4) Preparation of a cathode catalyst layer on a proton exchange membrane with a first catalyst slurry in a coating apparatus, load setting0.3mg/cm 2 The number of coating times was 3.
5) Turning the prepared cathode catalytic layer on a spraying device, and starting to prepare an anode catalytic layer on a proton exchange membrane by using second catalyst slurry in the spraying device, wherein the loading capacity is set to be 0.1mg/cm 2 Spraying times are 1 time;
6) And drying and taking down the CCM, and finishing the preparation, wherein the drying temperature is higher than 70 ℃.
Testing and characterization
1. The membrane electrode assembly MEA was prepared from the fuel cell membrane electrode CCM prepared in example 1, and the results obtained by sampling according to national standards are shown in FIG. 5. The fuel cell membrane electrode CCM prepared in comparative example 1 was prepared into a membrane electrode assembly MEA, and a sampling test was performed according to national standards, and the results are shown in FIG. 5.
2. The membrane electrode assembly MEA was prepared from the fuel cell membrane electrode CCM prepared in example 2, and the results obtained by sampling according to national standards are shown in FIG. 6. The fuel cell membrane electrode CCM prepared in comparative example 1 was prepared into a membrane electrode assembly MEA, and a sampling test was performed according to national standards, and the results are shown in FIG. 6.
As can be seen from fig. 5 and 6, the performance of the membrane electrode assembly MEA is obviously improved by adopting the fuel cell membrane electrode CCM prepared by the embodiment of the present application, which indicates that the fuel cell membrane electrode CCM prepared by the embodiment of the present application has better catalytic performance, stable structure, difficult falling off, and good durability.
3. The membrane electrode assemblies MEA were prepared from the fuel cell membrane electrode CCMs prepared in example 1, example 2, comparative example 1, and comparative example 2, respectively, and sampling tests were performed according to national standards.
The fuel cell membrane electrode CCM prepared in comparative example 1 and comparative example 2 was found to have inferior catalytic performance to those of example 1 and example 2.
Therefore, the first cathode catalyst layer and the second cathode catalyst layer have synergistic effect, so that the membrane electrode prepared by the embodiment of the application has excellent catalytic performance, surface performance, durability and the like.
In summary, the fuel cell membrane electrode prepared by the embodiment of the application is prepared into a two-layer structure by preparing the cathode catalyst layer; what should be stated here is: (1) The catalyst in the inner layer (first cathode catalyst layer) of the cathode catalyst layer adopts a catalyst with a three-dimensional network structure, so that the contact between an active substance and a current collector and a proton membrane is enhanced, a three-phase reaction area is increased, more reaction space is provided, the utilization rate of platinum is greatly improved, and the mass transfer efficiency and the power generation efficiency of the fuel cell are improved. (2) The inner layer of the cathode catalyst layer (the first cathode catalyst layer) is taken as a coating layer, and a coating process is selected according to the structure of the first cathode catalyst, so that the preparation efficiency can be greatly improved, and the mass production can be realized; (3) The catalyst in the inner layer of the cathode catalyst layer is a catalyst with a three-dimensional network structure, so that the mechanical strength of the catalyst layer is greatly enhanced, and meanwhile, the outer layer (the second cathode catalyst layer) of the cathode catalyst layer is a spray coating layer, so that the surface compactness of the cathode catalyst layer can be improved, the surface defect is reduced, and meanwhile, the semi-graphitized carrier has a certain improvement on the durability, so that the corrosion of the carbon carrier in the cathode catalyst layer by current can be well avoided, and the durability is greatly improved; (4) Although the outer layer of the cathode catalyst layer (second cathode catalyst layer) is a spray coating layer, the second cathode catalyst layer can be made thin due to the existence of the first cathode catalyst layer, so that the cathode catalyst layer is not affected by the thickness. In summary, the synergistic effect of the first cathode catalyst layer and the second cathode catalyst layer makes the cathode catalyst layer of the membrane electrode CCM have the characteristics of high mass transfer efficiency, good durability, low load and few surface defects.
The above description is only of the preferred embodiments of the present application, and is not intended to limit the present application in any way, but any simple modification, equivalent variation and modification made to the above embodiments according to the technical substance of the present application still fall within the scope of the technical solution of the present application.
Claims (31)
1. A membrane electrode CCM for use in a fuel cell, the membrane electrode CCM comprising a proton exchange membrane and a cathode catalyst layer coated on the proton exchange membrane; wherein the cathode catalyst layer comprises:
a first cathode catalyst layer coated on the proton exchange membrane; wherein the first cathode catalyst in the first cathode catalyst layer is a catalyst with a three-dimensional network structure;
a second cathode catalyst layer sprayed on the first cathode catalyst layer; wherein the second cathode catalyst in the second cathode catalyst layer is a granular catalyst;
wherein the first cathode catalyst is a composite carbon carrier supported alloy catalyst; wherein, in the composite carbon carrier supported alloy catalyst: the composite carbon carrier is a composite material comprising a granular carbon material and a linear carbon material; the alloy is platinum-cobalt alloy.
2. The membrane electrode CCM of claim 1 wherein in the composite carbon support supported alloy catalyst: the content of platinum in the platinum-cobalt alloy is 10-60wt%.
3. The membrane electrode CCM of claim 2 wherein in the composite carbon support supported alloy catalyst: the content of platinum in the platinum-cobalt alloy is 15-50wt%.
4. The membrane electrode CCM of claim 1 wherein in the composite carbon support supported alloy catalyst: the content of the platinum-cobalt alloy is 20-60wt%.
5. The membrane electrode CCM according to claim 1, wherein,
the granular carbon material is one or more of mesoporous carbon, carbon microsphere and amorphous carbon.
6. The membrane electrode CCM according to claim 1, wherein,
the linear carbon material is carbon nano tube and/or carbon fiber.
7. The membrane electrode CCM according to claim 1, wherein,
the first cathode catalyst layer has a loading of 0.1-0.2mg/cm 2 。
8. The membrane electrode CCM of claim 1 wherein the second cathode catalyst is selected from semi-graphitized pure platinum catalysts.
9. The membrane electrode CCM according to claim 8, wherein,
and the second cathode catalyst is a semi-graphitized pure platinum catalyst of TEC10EA50E type.
10. The membrane electrode CCM according to claim 8, wherein,
the second cathode catalyst layer has a loading of 0.1-0.2mg/cm 2 。
11. The membrane electrode CCM of claim 1 further comprising an anode catalyst layer sprayed on the proton exchange membrane; wherein,,
the anode catalyst in the anode catalyst layer is a granular catalyst.
12. The membrane electrode CCM according to claim 11, wherein,
the anode catalyst is a semi-graphitized pure platinum catalyst.
13. The membrane electrode CCM according to claim 11, wherein,
the anode catalyst layer has a loading of 0.1-0.2mg/cm 2 。
14. The method for preparing a membrane electrode CCM according to any one of claims 1 to 13, comprising the steps of:
preparing a first cathode catalyst layer: coating a first catalyst slurry on a first surface of a proton exchange membrane by adopting a coating process to form a first cathode catalyst layer;
preparing a second cathode catalyst layer: and spraying the second catalyst slurry on the first cathode catalyst layer by adopting a spraying process to form a second cathode catalyst layer.
15. The method for preparing a membrane electrode assembly CCM according to claim 14, wherein,
the first catalyst slurry comprises a first cathode catalyst and a solvent; wherein the solid content of the first catalyst slurry is 6-10wt%; the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol; wherein the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the alcohol is (1.5-2): (0.5-1): (3-5): (6-8).
16. The method for preparing a membrane electrode assembly CCM according to claim 14, wherein,
the second catalyst slurry comprises a second cathode catalyst and a solvent; wherein the solid content of the second catalyst slurry is 6-10wt%; the solvent comprises perfluorosulfonic acid solution, PTFE emulsion, deionized water and alcohol; wherein the mass ratio of the perfluorosulfonic acid solution to the PTFE emulsion to the deionized water to the alcohol is (1.5-2): (0.5-1): (3-5): (6-8).
17. The method of preparing a membrane electrode CCM according to claim 14, wherein the step of preparing a first cathode catalyst layer comprises:
the first catalyst sizing agent is added into preheated coating equipment after being subjected to ultrasonic dispersion; then, a first cathode catalyst layer is prepared on the first side of the proton exchange membrane using a coating apparatus.
18. The method for preparing a membrane electrode CCM according to claim 17, wherein,
the time for ultrasonic dispersion of the first catalyst slurry is 15-30min.
19. The method for preparing a membrane electrode CCM according to claim 17, wherein,
the coating equipment is sheet type coating equipment or roll-to-roll coating equipment.
20. The method for preparing a membrane electrode CCM according to claim 17, wherein,
when a coating device is used for preparing a first cathode catalyst layer on the first surface of the proton exchange membrane, the loading is set to be 0.1-0.2mg/cm 2 。
21. The method for preparing a membrane electrode CCM according to claim 17, wherein,
prior to the step of preparing the first cathode catalyst layer, comprising: cleaning and preheating coating equipment; wherein, the steps of cleaning and preheating comprise: and (3) cleaning the coating equipment by adopting ethanol, starting up for temperature debugging, setting the preheating temperature to be higher than 70 ℃, and finishing preheating after the temperature is stable.
22. The method of preparing a membrane electrode CCM according to claim 14, wherein the step of preparing a second cathode catalyst layer comprises:
the second catalyst slurry is added into preheated spraying equipment after being subjected to ultrasonic dispersion; then, a second cathode catalyst layer is prepared on the first cathode catalyst layer using a spray apparatus.
23. The method for preparing a membrane electrode assembly CCM according to claim 22,
the second catalyst slurry was subjected to ultrasonic dispersion for 15-30min.
24. The method for preparing a membrane electrode assembly CCM according to claim 22,
the spraying equipment is ultrasonic spraying equipment.
25. The method for preparing a membrane electrode assembly CCM according to claim 22,
when preparing the second cathode catalyst layer on the first cathode catalyst layer by using a spraying device, the loading is set to be 0.1-0.2mg/cm 2 。
26. The method for preparing a membrane electrode assembly CCM according to claim 22,
prior to the step of preparing the second cathode catalyst layer, comprising: cleaning and preheating the spraying equipment; wherein, the steps of cleaning and preheating comprise: and cleaning the spraying equipment by adopting ethanol, starting up for temperature adjustment, setting the preheating temperature to be higher than 70 ℃, and finishing preheating after the temperature is stable.
27. The method of preparing a membrane electrode CCM according to claim 14, further comprising:
preparing an anode catalyst layer: preparing an anode catalyst layer on the second surface of the proton exchange membrane by adopting spraying equipment, wherein the loading is set to be 0.1-0.2mg/cm 2 。
28. The method for preparing a membrane electrode CCM according to claim 27,
and after the preparation of the first cathode catalyst layer, the second cathode catalyst layer and the anode catalyst layer is finished, drying treatment is carried out to obtain the membrane electrode CCM.
29. The method for preparing a membrane electrode CCM according to claim 28,
the temperature of the drying treatment is higher than 70 ℃.
30. A membrane electrode assembly MEA, characterized in that it comprises a membrane electrode CCM according to any one of claims 1-13.
31. A fuel cell comprising the membrane electrode CCM of any one of claims 1-13 or the membrane electrode assembly MEA of claim 30.
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| CN116759590B (en) * | 2023-08-17 | 2023-10-31 | 安徽明天新能源科技有限公司 | Preparation method of multi-layer catalytic layer structure CCM |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1691383A (en) * | 2004-04-26 | 2005-11-02 | 株式会社东芝 | Anode for liquid fuel cell, membrane electrode assembly for liquid fuel cell, and liquid fuel cell |
| JP2008251549A (en) * | 2008-07-11 | 2008-10-16 | Toyota Motor Corp | Electrode catalyst structure as fuel cell membrane |
| JP2009117248A (en) * | 2007-11-08 | 2009-05-28 | Toshiba Corp | Fuel cell |
| JP2009170204A (en) * | 2008-01-15 | 2009-07-30 | Toshiba Corp | Membrane electrode assembly and fuel cell |
| JP2010123572A (en) * | 2008-10-22 | 2010-06-03 | Nippon Steel Corp | Fuel cell |
| CN102088092A (en) * | 2011-01-10 | 2011-06-08 | 北京科技大学 | Preparation method for three-dimensional network structure membrane electrode for direct methanol fuel cell |
| CN104979567A (en) * | 2015-06-19 | 2015-10-14 | 南京大学昆山创新研究院 | Production method of proton exchange membrane fuel cell membrane electrode |
| JP2018060716A (en) * | 2016-10-06 | 2018-04-12 | 株式会社フジクラ | Membrane-electrode assembly |
| JP2018206626A (en) * | 2017-06-06 | 2018-12-27 | 凸版印刷株式会社 | Membrane electrode assembly |
| CN109524674A (en) * | 2017-09-19 | 2019-03-26 | 粟青青 | The method for promoting fuel cell membrane electrode cathode catalysis layer performance |
| CN109863632A (en) * | 2016-09-30 | 2019-06-07 | 百拉得动力系统公司 | The cathode electrode of electrochemical fuel cell designs |
| CN111370717A (en) * | 2020-03-18 | 2020-07-03 | 浙江锋源氢能科技有限公司 | Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell |
| JP2020145044A (en) * | 2019-03-05 | 2020-09-10 | パナソニックＩｐマネジメント株式会社 | Cathode catalyst layer of fuel cell and fuel cell |
| CN113328106A (en) * | 2021-06-02 | 2021-08-31 | 永安行科技股份有限公司 | Fuel cell membrane electrode and preparation method and application thereof |
| CN113611874A (en) * | 2021-06-17 | 2021-11-05 | 苏州欣和智达能源科技有限公司 | Composite carbon carrier alloy catalyst and preparation method and application thereof |
| CN114068955A (en) * | 2021-10-29 | 2022-02-18 | 浙江天能氢能源科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4974403B2 (en) * | 2000-05-31 | 2012-07-11 | 日本ゴア株式会社 | Solid polymer electrolyte fuel cell |
| US9346673B2 (en) * | 2004-06-23 | 2016-05-24 | Samsung Sdi Co., Ltd. | Electrode for fuel cell, membrane-electrode assembly for fuel cell comprising the same, fuel cell system comprising the same, and method for preparing the electrode |
| KR100908720B1 (en) * | 2007-09-14 | 2009-07-22 | 삼성에스디아이 주식회사 | Membrane-electrode assembly for fuel cell, and fuel cell system comprising same |
| US20090081510A1 (en) * | 2007-09-26 | 2009-03-26 | Kabushiki Kaisha Toshiba | Supported catalyst, method for manufacturing supported catalyst, fuel cell, and method for manufacturing fuel cell |
| JP2012508433A (en) * | 2008-11-07 | 2012-04-05 | ナショナル・リサーチ・カウンシル・オブ・カナダ | Catalyst material for fuel cell electrode and method for producing the same |
| US9941523B2 (en) * | 2011-07-18 | 2018-04-10 | Daimler Ag | Bilayer cathode catalyst structure for solid polymer electrolyte fuel cell |
| US10205173B2 (en) * | 2014-07-08 | 2019-02-12 | Bdf Ip Holdings Ltd. | Cathode design for electrochemical cells |
-
2022
- 2022-06-28 CN CN202210741531.0A patent/CN115064710B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1691383A (en) * | 2004-04-26 | 2005-11-02 | 株式会社东芝 | Anode for liquid fuel cell, membrane electrode assembly for liquid fuel cell, and liquid fuel cell |
| JP2009117248A (en) * | 2007-11-08 | 2009-05-28 | Toshiba Corp | Fuel cell |
| JP2009170204A (en) * | 2008-01-15 | 2009-07-30 | Toshiba Corp | Membrane electrode assembly and fuel cell |
| JP2008251549A (en) * | 2008-07-11 | 2008-10-16 | Toyota Motor Corp | Electrode catalyst structure as fuel cell membrane |
| JP2010123572A (en) * | 2008-10-22 | 2010-06-03 | Nippon Steel Corp | Fuel cell |
| CN102088092A (en) * | 2011-01-10 | 2011-06-08 | 北京科技大学 | Preparation method for three-dimensional network structure membrane electrode for direct methanol fuel cell |
| CN104979567A (en) * | 2015-06-19 | 2015-10-14 | 南京大学昆山创新研究院 | Production method of proton exchange membrane fuel cell membrane electrode |
| CN109863632A (en) * | 2016-09-30 | 2019-06-07 | 百拉得动力系统公司 | The cathode electrode of electrochemical fuel cell designs |
| JP2018060716A (en) * | 2016-10-06 | 2018-04-12 | 株式会社フジクラ | Membrane-electrode assembly |
| JP2018206626A (en) * | 2017-06-06 | 2018-12-27 | 凸版印刷株式会社 | Membrane electrode assembly |
| CN109524674A (en) * | 2017-09-19 | 2019-03-26 | 粟青青 | The method for promoting fuel cell membrane electrode cathode catalysis layer performance |
| JP2020145044A (en) * | 2019-03-05 | 2020-09-10 | パナソニックＩｐマネジメント株式会社 | Cathode catalyst layer of fuel cell and fuel cell |
| CN111370717A (en) * | 2020-03-18 | 2020-07-03 | 浙江锋源氢能科技有限公司 | Cathode catalyst slurry, cathode catalyst layer, membrane electrode and fuel cell |
| CN113328106A (en) * | 2021-06-02 | 2021-08-31 | 永安行科技股份有限公司 | Fuel cell membrane electrode and preparation method and application thereof |
| CN113611874A (en) * | 2021-06-17 | 2021-11-05 | 苏州欣和智达能源科技有限公司 | Composite carbon carrier alloy catalyst and preparation method and application thereof |
| CN114068955A (en) * | 2021-10-29 | 2022-02-18 | 浙江天能氢能源科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| PEMFC阴极催化层结构分析;王睿卿等;电化学;第27卷(第6期);全文 * |
| 微型DMFC用新型双催化层膜电极的制备;索春光;张文斌;王华;文斯;;江苏大学学报(自然科学版)(第06期);全文 * |
| 高性能高功率密度质子交换膜燃料电池膜电极;池滨;侯三英;刘广智;廖世军;;化学进展(第Z1期);全文 * |
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