CN114628750A - Membrane electrode assembly and preparation method and application thereof - Google Patents
Membrane electrode assembly and preparation method and application thereof Download PDFInfo
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- CN114628750A CN114628750A CN202011462101.2A CN202011462101A CN114628750A CN 114628750 A CN114628750 A CN 114628750A CN 202011462101 A CN202011462101 A CN 202011462101A CN 114628750 A CN114628750 A CN 114628750A
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses a membrane electrode assembly and a preparation method and application thereof. The preparation method of the membrane electrode assembly comprises the following steps: providing an ion exchange membrane, wherein at least one side surface of the ion exchange membrane is provided with an array structure, and the array structure comprises a plurality of protrusions distributed in an array; and at least a catalyst and an electronic conductor are sequentially loaded on the array structure. The method for preparing the membrane electrode assembly by constructing the three-phase interface through magnetron sputtering supported catalyst and spraying the electronic conductor can greatly increase the three-phase interface (electrons, protons and mass transfer) in the catalyst layer to form a channel for quickly transferring reactants, protons and electrons, is beneficial to reducing the catalyst loading capacity, improving the catalyst utilization rate and improving the performance and the stability.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a membrane electrode assembly and a preparation method and application thereof.
Background
The electrolytic cell and the fuel cell are used as chemical energy and electric energy conversion devices for clean energy preparation and application, and have important significance for relieving energy crisis and reducing greenhouse gas emission. Both have many similarities in structure.
As for a fuel cell, it is expected to become a mainstream of future energy supply equipment as a power supply equipment having many advantages of high energy density, rapid start, high conversion efficiency, zero emission, and the like. However, the high cost of fuel cells, particularly their use of noble metal catalysts, has in the late past prevented widespread commercialization of fuel cells. Therefore, reducing the amount of noble metal catalyst, increasing the utilization rate of the catalyst, and simultaneously ensuring the performance and stability of the fuel cell are of great significance for the commercialization of the fuel cell.
The noble metal catalyst is positioned in a catalytic layer of the membrane electrode assembly, and the catalytic layer is a core part of the fuel cell for converting chemical energy into electric energy. The catalytic layer generally consists of a noble metal catalyst dispersed on carbon with high specific surface area, a hydrophobic agent (polytetrafluoroethylene) and a proton conductor (generally perfluorosulfonic acid resin). The excellent catalyst layer needs to satisfy the good transfer of reactants, protons, and electrons. However, in order to achieve high proton conductivity, an effective proton transport network is constructed, and a part of the catalyst is inevitably covered with a proton conductor, so that it is difficult to achieve a catalytic action, and the utilization rate of the catalyst is lowered. Therefore, how to simultaneously ensure the rapid progress of proton, electron and mass transfer is an important problem to be considered for improving the performance of the fuel cell and reducing the catalyst loading capacity of the fuel cell.
The thin-layer catalyst layer based on the micro-nano structure is proved to be expected to solve the problem. Some documents prepare ion exchange membranes containing array structures by means of nanoimprint lithography, electron beam etching and the like, and the shape, the length-diameter ratio and the density of the array can be regulated and controlled. The array structure ion exchange membrane can increase three-phase interfaces (mass transfer, electrons and protons), reduce the coverage of a proton conductor on a catalyst, and simultaneously construct a rapid proton transfer channel, thereby being beneficial to the improvement of the performance of a battery.
However, when the ion exchange membrane with the array structure is used in a fuel cell, the performance of the cell is not greatly improved and does not reach a higher level. The main reason is that the loading of the catalyst in such array structures is often to directly load the carbon supported catalyst (Pt/C), the catalyst is mostly concentrated at the top end of the array, and is difficult to enter the inside of the array to achieve good contact between the array and the catalyst, and meanwhile, the inside of the catalyst does not really form an effective proton transfer network. The loading mode of the catalyst is difficult to play the role of the array structure ion exchange membrane really, and further the purposes of reducing the catalyst loading capacity, improving the catalyst utilization rate and improving the performance of the fuel cell are achieved. Therefore, the effective load of the catalyst on the ion exchange membrane with the array structure, the real mass transfer and the construction of the fast electron proton transfer channel need to be improved.
Disclosure of Invention
The invention mainly aims to provide a membrane electrode assembly, a preparation method and application thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a membrane electrode assembly, which comprises the following steps:
providing an ion exchange membrane, wherein at least one side surface of the ion exchange membrane is provided with an array structure, and the array structure comprises a plurality of micro-nano protrusions distributed in an array;
and at least a catalyst and an electronic conductor are sequentially loaded on the array structure.
Further, the preparation method of the membrane electrode assembly comprises the following steps: the array structure is directly grown on the surface of the ion exchange membrane or is processed on the surface of the ion exchange membrane by any one mode of transfer printing, nano imprinting and electron beam etching.
Further, the preparation method of the membrane electrode assembly comprises the following steps: loading a catalyst on the surface of the ion exchange membrane with an array structure at least in a magnetron sputtering mode;
and/or loading an electronic conductor on the surface of the ion exchange membrane with the array structure at least by a spraying mode.
Further, the preparation method of the membrane electrode assembly comprises the following steps: spraying powdered electronic conductors or a dispersion of electronic conductors onto the surface of the ion exchange membrane having an array structure, thereby loading the electronic conductors at least on the surface and/or inside the array structure.
Further, the preparation method of the membrane electrode assembly further comprises the following steps: compounding an ion exchange membrane loaded with a catalyst and an electronic conductor with gas diffusion layers, and placing one of the ion exchange membranes loaded with the catalyst and the electronic conductor between the two gas diffusion layers; preferably, the gas diffusion layer comprises a carbon paper electrode.
Still further, the method for preparing the membrane electrode assembly further comprises: a catalyst is supported on one of the gas diffusion layers, and the catalyst-supported gas diffusion layer is made to face away from the surface of the ion-exchange membrane on the side on which the catalyst and the electron conductor are supported.
The embodiment of the invention also provides a membrane electrode assembly prepared by the method.
The embodiment of the invention also provides an application of the membrane electrode assembly in preparing an electrochemical device.
Accordingly, embodiments of the present invention provide a fuel cell including the membrane electrode assembly described above.
The embodiment of the invention also provides an electrolytic cell, which comprises the membrane electrode assembly.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the membrane electrode assembly of the invention constructs a three-phase interface by magnetron sputtering load catalyst and spraying electronic conductor to prepare the membrane electrode assembly, can greatly increase the three-phase interface (electron, proton and mass transfer) in the catalyst layer, form a channel for fast transferring reactant, proton and electron, is beneficial to reducing the catalyst loading capacity, improving the catalyst utilization rate, improving the performance and stability, can be prepared in large scale, and is beneficial to the commercialization of electrochemical devices such as fuel cells, electrolytic cells and the like.
(2) The preparation method of the membrane electrode assembly can realize the loading of the catalyst on the ion exchange membrane with the array structure by adopting magnetron sputtering, the magnetron sputtering can ensure that the catalyst is uniformly loaded on the array membrane, and meanwhile, the type, the loading capacity, the particle size and the loading position of the catalyst can be accurately regulated and controlled, and the high-speed transfer of protons and the high-efficiency utilization of the catalyst are realized.
(3) The preparation method of the membrane electrode assembly realizes the load of an electronic conductor by spraying a conductive material, realizes the effective construction of an electronic transmission network in an array, and can greatly increase a three-phase interface (electron, proton and mass transfer); meanwhile, the types, sizes, load capacity and load positions of the electronic conductors are adjustable and controllable.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flowchart of a method for producing a membrane electrode assembly in example 1 of the present application.
Fig. 2a is an SEM picture of Pt nanoparticles supported by the array film according to an embodiment of the present disclosure, and fig. 2b is an EDX spectrum of Pt nanoparticles supported by the array film according to an embodiment of the present disclosure.
Fig. 3 is an SEM picture of the array film supporting Pt nanoparticles and graphene in an embodiment of the present application.
Fig. 4 is a polarization curve of the membrane electrode assembly used in the proton exchange membrane fuel cell in example 1 of this application.
Fig. 5 is a stability test chart of the membrane electrode assembly used in the proton exchange membrane fuel cell in example 1 of the present application.
FIG. 6 is a flowchart of a method for producing a membrane electrode assembly in example 2 of the present application.
Fig. 7 is a polarization curve of the membrane electrode assembly used in the proton exchange membrane fuel cell in example 2 of this application.
Fig. 8 is a stability test chart of the membrane electrode assembly used in the proton exchange membrane fuel cell in example 2 of the present application.
FIG. 9 is an SEM photograph of a proton exchange membrane in comparative example 1 of the present application.
FIG. 10 is a polarization curve of a proton exchange membrane fuel cell in comparative example 1 of the present application.
FIG. 11 is a graph showing stability tests of a proton exchange membrane fuel cell in comparative example 1 of the present application.
Fig. 12 is a polarization curve of a pem fuel cell with different graphene contents in comparative example 2 of the present application.
Fig. 13 is a polarization curve of the membrane electrode assembly for a proton exchange membrane fuel cell in example 3 of this application.
Fig. 14 is a polarization curve of the membrane electrode assembly for a proton exchange membrane fuel cell in example 4 of this application.
Description of the reference numerals: 1. the catalyst comprises a proton exchange membrane, 11, an array structure, 2, Pt nanoparticles, 3, graphene slurry, 4, a carbon paper electrode and 5, a Pt/C catalyst.
Detailed Description
The invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The invention mainly uses magnetron sputtering to load catalyst, and sprays electronic conductor to construct three-phase interface to prepare membrane electrode assembly, which can greatly increase three-phase interface (electron, proton, mass transfer) in the catalyst layer to form a channel for fast transferring reactant, proton and electron, which is beneficial to reducing catalyst loading capacity, improving catalyst utilization rate, and improving performance and stability.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of an embodiment of the present invention provides a method for preparing a membrane electrode assembly, including the steps of:
providing an ion exchange membrane, wherein at least one side surface of the ion exchange membrane is provided with an array structure, and the array structure comprises a plurality of protrusions distributed in an array;
and at least a catalyst and an electronic conductor are sequentially loaded on the array structure.
In some preferred embodiments, the method for preparing a membrane electrode assembly includes: the array structure is directly grown on the surface of the ion exchange membrane or processed on the surface of the ion exchange membrane by at least any one of transfer printing, nano imprinting and electron beam etching.
Accordingly, the shape of the protrusion may include any one or a combination of more of a cone, a rectangle, a cylinder, a Y-shape, a branch shape, etc., but is not limited thereto; preferably, the protrusion is tapered, the height of the taper is 0.5-2.5 μm, the upper diameter of the taper is 100-400nm, the lower diameter of the taper is 400-700nm, and the distance between the tapers is 450-800 nm.
In some preferred embodiments, the method for preparing a membrane electrode assembly includes: loading a catalyst on the surface of the ion exchange membrane with an array structure at least in a magnetron sputtering mode;
and loading an electronic conductor on the surface of the ion exchange membrane with the array structure at least in a spraying mode.
In the implementation process, the catalyst can be loaded by magnetron sputtering of a single target, or by simultaneous sputtering of a plurality of targets, or by sequential sputtering of a plurality of targets, the catalyst with non-single component can adjust the proportion of different components through the sputtering time, the size of the catalyst can be adjusted by the current of magnetron sputtering, and the current is adjusted to 5-200 mA; the loading capacity of the catalyst can be adjusted by the sputtering time, and the loading capacity can be accurate to mu gcm-2The loading area of the catalyst can be adjusted,the method can be realized by replacing targets with different areas, or batch loading can be carried out on different areas under the same target, and the loading position of the catalyst can be adjusted by the angles of the magnetron sputtering target and the array film.
In the embodiment of the invention, the loading of the catalyst on the ion exchange membrane with the array structure can be realized by adopting magnetron sputtering, the magnetron sputtering can ensure that the catalyst is uniformly loaded on the array membrane, and meanwhile, the type, the loading capacity, the particle size and the loading position of the catalyst can be accurately regulated and controlled, and the high-speed transfer of protons and the high-efficiency utilization of the catalyst are realized.
Correspondingly, the target material adopted by the magnetron sputtering method can include any one or a combination of more than one of a single metal target, an alloy target, a compound target and the like, but is not limited to the above; the single metal target comprises Pt or Ru, the alloy target comprises PtCo, PtNi or PtRu, and the compound target comprises MoS2Or IrO2。
Correspondingly, the current intensity adopted by the magnetron sputtering mode is 5-200mA, and the magnetron sputtering mode comprises the following steps: magnetron sputtering is carried out by adopting a single target material, or sputtering is carried out by adopting a plurality of target materials simultaneously or sequentially.
In some preferred embodiments, the method for preparing a membrane electrode assembly includes: spraying powdered electronic conductors or a dispersion of electronic conductors onto the surface of the ion exchange membrane having an array structure, thereby loading the electronic conductors at least on the surface and/or inside the array structure.
Accordingly, the electron conductor may include any one or a combination of more of carbon nanotubes, graphene oxide, graphene nanoplatelets, and the like, but is not limited thereto.
Accordingly, the solvent in the dispersion of the electron conductor includes water and/or an organic solvent.
The loading capacity of the electronic conductor on the array membrane can be adjusted by changing the spraying volume, and the loading capacity can be accurate to mu gcm-2The position of the electronic conductor on the array film can be adjusted by changing the size of the electronic conductorThe top of the array may also be internal to the array.
In the embodiment of the invention, the load of the electronic conductor is realized by spraying the conductive material, the effective construction of the electronic transmission network in the array is realized, and the three-phase interface (electron, proton and mass transfer) can be greatly increased; meanwhile, the type, size, load capacity and load position of the electronic conductor are adjustable and controllable.
In some preferred embodiments, the method for preparing a membrane electrode assembly further comprises: compounding an ion exchange membrane loaded with a catalyst and an electronic conductor with gas diffusion layers, and placing one of the ion exchange membranes loaded with the catalyst and the electronic conductor between the two gas diffusion layers; preferably, the gas diffusion layer comprises a carbon paper electrode.
In some preferred embodiments, the method for preparing a membrane electrode assembly further comprises: a catalyst is supported on one of the gas diffusion layers, and the catalyst-supported gas diffusion layer is made to face away from the surface of the ion-exchange membrane on the side on which the catalyst and the electron conductor are supported.
In some preferred embodiments, the electron conductor may include, but is not limited to, carbon nanotubes, graphene oxide, and the like.
In some preferred embodiments, the electronic conductor is in a powder form or uniformly dispersed in a solvent, and the solvent includes deionized water or an organic solvent, preferably, the organic solvent may include ethanol or acetone, but is not limited thereto.
Another aspect of the embodiments of the present invention also provides a membrane electrode assembly prepared by the foregoing method.
Another aspect of the embodiments of the present invention also provides an application of the aforementioned membrane electrode assembly in an electrochemical device.
In another aspect, the present invention also provides a fuel cell (such as a proton exchange membrane fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, an alkaline fuel cell, and other different types of fuel cells) comprising the aforementioned membrane electrode assembly.
In another aspect, the embodiment of the invention further provides an electrolytic cell (such as a water electrolysis hydrogen production device) comprising the membrane electrode assembly.
The membrane electrode assembly provided by the embodiment of the invention can be used on the anode side, the cathode side or both sides of the fuel cell, the electrolytic cell or other electrochemical reaction devices.
As one of the preferred embodiments, the method for preparing a membrane electrode assembly according to an embodiment of the present invention may include:
(1) the ion exchange membrane comprises an array structure, wherein the array structure can be in different shapes (conical shape, rectangular shape, cylindrical shape and the like), can be in different length-diameter ratios, can be in different densities, can be positioned on one side of the ion exchange membrane, and can also be positioned on two sides of the ion exchange membrane simultaneously.
(2) Loading of the catalyst: flatly laying and fixing an ion exchange membrane containing an array structure on a clean glass sheet; the catalyst is placed in a magnetron sputtering cavity and is positioned right below a sputtering target, and the particle size and the loading amount of a sputtering catalyst are adjusted by adjusting the sputtering time and the sputtering current.
(3) Loading of the electronic conductor: the ion exchange membrane loaded with the catalyst is taken out of the magnetron sputtering cavity, electronic conductor slurry which is uniformly dispersed is sprayed on the ion exchange membrane through spraying, the loading position of the electronic conductor on the array membrane is adjusted through adjusting the size of the electronic conductor, and the loading capacity of the electronic conductor is adjusted through adjusting the volume of the slurry sprayed with the electronic conductor.
(4) And placing the ion exchange membrane loaded with the catalyst and the electronic conductor into two carbon paper electrodes, wherein the carbon paper electrode close to one side of the array structure has no catalyst load, the carbon paper electrode far away from one side of the array structure is loaded with the Pt/C catalyst, and the carbon paper electrodes are subjected to hot-pressing treatment to prepare the membrane-forming electrode assembly.
As a preferred embodiment, the array morphology of the ion exchange membrane with the array structure is conical,the height of the cone was 1.5 μm, the upper diameter of the cone was 100nm, the lower diameter of the cone was 400nm, and the spacing between cones was 450 nm. The magnetron sputtering target is a Pt target, the sputtering current is 20mA, the sputtering time is 8min, and the corresponding loading amount of Pt is 17.6 mu gcm-2. The electronic conductor is graphene, the size of the loaded graphene is 100nm, and the loading capacity is 7.9 mu gcm-2. And preparing a membrane electrode assembly by using one side loaded with Pt particles and graphene as one side of a proton exchange membrane and the other side loaded with a Pt/C catalyst, using one side of an array structure as an anode side and one side of a non-array structure as a cathode side, and applying the membrane electrode assembly to a proton exchange membrane fuel cell.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The preparation process of a membrane electrode assembly provided by this embodiment is shown in fig. 1, and includes the following steps:
(1) selecting a proton exchange membrane 1 with an array structure 11 on one side, wherein the shape of the array structure 11 is a cone, the height of the cone is 1.5 mu m, the upper diameter of the cone is 100nm, the lower diameter of the cone is 400nm, and the distance between the cones is 450 nm;
(2) the proton exchange membrane 1 containing the array structure 11 is flatly laid and fixed on a clean glass sheet; placing the target material in a magnetron sputtering cavity, wherein the target material is a Pt target and is positioned right below a sputtering target, the sputtering current is 20mA, the sputtering time is 8min, and the corresponding loading capacity of Pt is 17.6 mu gcm-2；
(3) Taking out the proton exchange membrane 1 loaded with the Pt nano particles 2 (shown in figure 2a, and clearly seen from EDX analysis in figure 2b, which proves that Pt is well loaded on a Nafion array) from a magnetron sputtering cavity, spraying uniformly dispersed graphene slurry 3 on the proton exchange membrane 1 by spraying, so that the graphene slurry 3 is loaded at the top end or inside of the array structure 11 (shown in figure 3, clearly seen from figure 3 that graphene nano sheets are uniformly interspersed among the Nafion arrays), and constructing a good proton exchange membraneElectron transport network), the size of the loaded graphene is 100nm, and the loading capacity is 7.9 mu gcm-2；
(4) The proton exchange membrane 1 loaded with the Pt nano particles 2 and the graphene is placed in two carbon paper electrodes 4, wherein the carbon paper electrode 4 close to one side of the array structure 11 has no catalyst load, the carbon paper electrode 4 far away from one side of the array structure 11 is loaded with a Pt/C catalyst 5, and the carbon paper electrode is subjected to hot-pressing treatment to prepare a membrane-forming electrode assembly.
The obtained membrane electrode assembly is assembled into a single cell to carry out proton exchange membrane fuel cell performance test, the polarization curve is shown in figure 4, the open-circuit voltage of the cell is about 1.0V, and the peak power of the cell is 1.24W cm-2Indicating that the battery has a higher discharge capacity at lower loadings. Stability test As shown in FIG. 5, the cell was operated at 50mA cm-2The lower constant current discharge for 300h has no obvious voltage attenuation and shows excellent stability.
Example 2
The preparation process of a membrane electrode assembly provided by this embodiment is shown in fig. 6, and includes the following steps:
(1) selecting a proton exchange membrane 1 with array structures 11 on two sides, wherein the shape of the array structures 11 is a cone, the height of the cone is 1.5 mu m, the upper diameter of the cone is 100nm, the lower diameter of the cone is 400nm, and the distance between the cones is 450 nm;
(2) the proton exchange membrane 1 containing the array structure 11 is placed in a magnetron sputtering cavity and is positioned right below a sputtering target, the target material is a Pt target, the sputtering current is 20mA, the sputtering time is 8min, and the corresponding loading capacity of Pt is 17.6 mu gcm-2；
(3) Taking out the proton exchange membrane 1 loaded with the Pt nano particles 2 from the magnetron sputtering cavity, spraying uniformly dispersed graphene slurry 3 on the proton exchange membrane 1 by spraying, and enabling the graphene slurry 3 to be loaded at the top end or inside the array structure 11, wherein the size of the loaded graphene is 100nm, and the loading amount is 7.9 mu gcm-2；
(4) And (3) placing the Pt nano-particles 2 and the graphene loaded proton exchange membrane 1 into two carbon paper electrodes 4, and performing hot-pressing treatment on the two carbon paper electrodes to prepare a membrane-forming electrode assembly.
The obtained membrane electrode assembly is assembled into a single cell to carry out proton exchange membrane fuel cell performance test, the polarization curve is shown in figure 7, the open-circuit voltage of the cell is about 1.0V, and the peak power of the cell is 0.65W cm-2Indicating that the battery has a higher discharge capacity at lower loadings. Stability testing As shown in FIG. 8, the cells were tested at 50mA cm-2The lower constant current discharge for 300h has no obvious voltage attenuation and shows excellent stability.
Example 3
The embodiment provides a preparation method of a membrane electrode assembly, which comprises the following steps:
(1) the proton exchange membrane 1 with the array structures 11 on two sides is selected, the shape of the array structures 11 is conical, the heights of the cones are respectively 0.5 mu m, 0.9 mu m, 1.5 mu m and 2.5 mu m, the upper diameter of each cone is 100nm, the lower diameter of each cone is 400nm, and the distance between the cones is 450 nm.
(2) And (3) the same as in embodiment 1.
(4) The same as in embodiment 1.
The membrane electrode assembly obtained is assembled into a single cell to be tested for the performance of the proton exchange membrane fuel cell, the polarization curve is shown in figure 13, the cells with different array lengths have obvious performance difference, and the preferred length is 1.5 μm.
Example 4
(1) The same as embodiment 1;
(2) the proton exchange membrane 1 containing the array structure 11 is flatly laid and fixed on a clean glass sheet; placing the target material in a magnetron sputtering cavity and under a sputtering target, wherein the target material is a Pt target, the sputtering current is 20mA, and the sputtering time is changed to obtain different Pt loading amounts;
(3) and (4) the same as in embodiment 1.
The membrane electrode assembly obtained is assembled into a single cell to carry out proton exchange membrane fuel cell performance test, the polarization curve is shown in figure 14, the cells with different Pt loading amounts have obvious performance difference, and the preferred loading amount is 17.6 mu gcm-2。
Comparative example 1
The comparative example is basically the same as example 1, but the proton exchange membrane adopted has a flat surface and no array structure; the proton exchange membrane structure is shown in fig. 9, and it can be seen from SEM that the proton exchange membrane without the array structure is relatively flat; as shown in FIG. 10, the open circuit voltage of the battery was about 1.0V, and the peak power of the battery was 0.5W cm-2The method shows that the battery without the array structure has weaker discharge capacity under lower loading capacity; the stability of the cell is shown in FIG. 11, the cell is at 50mA cm-2The lower constant current discharge for 150h shows larger performance attenuation and poorer stability. .
Comparative example 2
This comparative example is substantially the same as example 1, except that step (3) is omitted; as shown in fig. 12, the performance of the fuel cell is obviously affected by the content of graphene under different loading amounts, and the performance of the fuel cell can be further improved by appropriate loading amount of graphene.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure (invention) is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing or comprising specific components or where a process is described as having, containing or comprising specific process steps, it is contemplated that the composition taught by the present invention also consists essentially of or consists of the recited components and the process taught by the present invention also consists essentially of or consists of the recited process steps.
Unless specifically stated otherwise, use of the terms "comprising", "including", "having" or "having" is generally to be understood as open-ended and not limiting.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for preparing a membrane electrode assembly, comprising the steps of:
providing an ion exchange membrane, wherein at least one side surface of the ion exchange membrane is provided with an array structure, and the array structure comprises a plurality of micro-nano protrusions distributed in an array manner;
and at least a catalyst and an electronic conductor are sequentially loaded on the array structure.
2. The method of producing a membrane electrode assembly according to claim 1, characterized by comprising: the array structure is directly grown on the surface of the ion exchange membrane or is processed on the surface of the ion exchange membrane at least in any one mode of transfer printing, nanoimprint lithography and electron beam etching to form the array structure;
and/or the shape of the protrusion part comprises any one or combination of more of a cone shape, a rectangle shape, a column shape, a Y shape and a branch shape; preferably, the protrusion is tapered, the height of the taper is 0.5-2.5 μm, the upper diameter of the taper is 100-400nm, the lower diameter of the taper is 400-700nm, and the distance between the tapers is 450-800 nm.
3. The method of producing a membrane electrode assembly according to claim 1, characterized by comprising: loading a catalyst on the surface of the ion exchange membrane with an array structure at least in a magnetron sputtering mode;
and/or, loading an electronic conductor on the surface of the ion exchange membrane with an array structure at least by a spraying mode;
and/or the target material adopted by the magnetron sputtering mode comprises one or more of a single metal target, an alloy target or a compound target, wherein the single metal target comprises Pt or Ru, the alloy target comprises PtCo, PtNi or PtRu, and the compound target comprises MoS2Or IrO2(ii) a And/or the current intensity adopted by the magnetron sputtering mode is 5-200 mA; and/or the magnetron sputtering mode comprises the following steps: magnetron sputtering is carried out by adopting a single target material, or sputtering is carried out by adopting a plurality of target materials simultaneously or sequentially.
4. The method of producing a membrane electrode assembly according to claim 1, characterized by comprising: spraying a powdered electronic conductor or a dispersion of an electronic conductor onto the surface of the ion exchange membrane having an array structure, thereby loading the electronic conductor at least on the surface and/or inside the array structure;
and/or the electronic conductor comprises any one or combination of more of carbon nano tubes, graphene oxide, oxygen reduction graphene and graphene micro-sheets; and/or the solvent in the dispersion of the electronic conductor comprises water and/or an organic solvent.
5. The method of producing a membrane electrode assembly according to claim 1, characterized by further comprising: compounding an ion exchange membrane loaded with a catalyst and an electronic conductor with gas diffusion layers, and placing one of the ion exchange membranes loaded with the catalyst and the electronic conductor between the two gas diffusion layers; preferably, the gas diffusion layer comprises a carbon paper electrode.
6. The method of producing a membrane electrode assembly according to claim 1, characterized by further comprising: a catalyst is supported on one of the gas diffusion layers, and the catalyst-supported gas diffusion layer is made to face away from the surface of the ion-exchange membrane on the side on which the catalyst and the electron conductor are supported.
7. A membrane electrode assembly prepared by the method of any one of claims 1 to 6.
8. Use of the membrane electrode assembly of claim 7 for the preparation of an electrochemical device.
9. A fuel cell comprising the membrane electrode assembly according to claim 7.
10. An electrolytic cell characterized by comprising the membrane electrode assembly according to claim 7.
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| CN106887598A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of ordering membrane electrode and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115627004A (en) * | 2022-10-17 | 2023-01-20 | 浙江理工大学 | Preparation method of high-permeability and high-biological antifouling ion exchange film |
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