CN116435560A - Batch preparation process of polymer electrolyte ordered large-area membrane electrode - Google Patents
Batch preparation process of polymer electrolyte ordered large-area membrane electrode Download PDFInfo
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Classifications
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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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/70—Maintenance
- B29C33/72—Cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/26—Component parts, details or accessories; Auxiliary operations
- B29C51/30—Moulds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A batch preparation process of a polymer electrolyte ordered large-area membrane electrode, comprising: 1. feed (polymer electrolyte membrane); 2. rolling (polymer electrolyte array film); 3. catalytic layer preparation (catalytic layer with array features); 4. cutting into slices (catalytic layer CCM under set size); 5. hot-pressing and packaging (hot-pressing and edge sealing to prepare the membrane electrode MEA). The method can be used for mass production of the polymer electrolyte ordered large-area membrane electrode, is applied to a fuel cell or an electrolytic cell, greatly improves the production efficiency of the ordered membrane electrode, ensures the consistency of the membrane electrode, and can reduce the production cost of the membrane electrode by mass preparation of the ordered membrane electrode. The prepared membrane electrode has excellent performance, and has high-efficiency and ordered gas, electron and ion transmission channels, so that a three-phase reaction interface is optimized, and the electrical performance is greatly improved.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to an actual production and application process of an ordered membrane electrode of a polymer electrolyte fuel cell or an electrolytic cell.
Background
The fuel cell is a clean and environment-friendly energy conversion device, can directly convert chemical energy of fuel into electric energy, can directly use hydrogen as fuel, can reform organic compounds and the like to be used as fuel, has a structure similar to that of the fuel cell, and can produce hydrogen by electrolysis of water. The polymer electrolyte fuel cell (Ploymer Electrolyte Fuel Cell, PEFC) such as proton exchange membrane fuel cell and alkaline membrane fuel cell has the advantages of simple structure, environmental friendliness, no pollution, higher efficiency, low working temperature and the like, is particularly suitable for portable power supplies, electric vehicle power supplies, distributed power stations, energy storage systems and the like, and has wide application prospect. The core component is a membrane electrode (Membrane Electrode Assembly, MEA), which is one of the decisive factors in the aspects of service life, cost, reliability and the like of the electrochemical reactor.
The MEA is mainly composed of anode and polymer membrane as cathode, wherein the core of the cathode and anode is a catalytic layer composed of catalyst with good electron conductivity (such as Pt, ru, ag, ni, mnO 2 、RuO 2 、IrO 2 And a supported catalyst and a composite catalyst containing the above metals or oxides) and a polymer solution having good ion conductivity (e.g., a solution composed of an anion exchange resin or a cation exchange resin); the polymer membrane mainly refers to a polymer electrolyte material (ion exchange membrane, also called polymer electrolyte membrane) having good ion conductivity. The development of membrane electrodes has undergone three stages: firstly, the catalyst is prepared on the surface of a Gas Diffusion Layer (GDL) by a hot-pressing method, the catalyst is prepared on the surface of the GDL by screen printing, spraying, coating, casting and other methods, the polymer electrolyte solution is soaked, and the catalyst is dried and then is put on two sides of a polymer electrolyte membrane, and the MEA is formed by hot pressing. The method is simple in preparation in technology, but the combination property of the catalytic layer and the polymer electrolyte membrane is poor; secondly, the catalyst sizing agent is directly sprayed on the polymer electrolyte membrane by using a spraying method or a transfer printing method, and compared with the first method, the method can effectively improve the space between the polymer electrolyte membrane and the catalytic layerIs used for the binding capacity of the polymer. However, in both of these preparation methods, the catalytic layer is a random mixture of an electron conductor (catalyst and its support) and an ion conductor (polymer solution) to form a heterogeneous mass transport of gas, protons, electrons, water, etc. However, the mass transfer channels are disordered, the catalytic activity of the catalyst cannot be fully exerted, and the long-term stability of the MEA is seriously affected due to severe electrochemical polarization and concentration polarization. Therefore, a new structure, i.e., an ordered membrane electrode, has been proposed for this phenomenon.
The basic constitution concept of the ordered membrane electrode is as follows: the electron, proton and gas transmission channels are separated, so that the electrochemical reaction active area in the electrode is effectively improved. The three-dimensional catalysis layer structure can improve the utilization rate of noble metal catalysts and polymer electrolyte solution, reduce catalyst loading and prolong battery life.
As early as 2002, erik et al (Fuel cell bulletin, 2002, 11:9-12) proposed a multiphase material transport channel ordering structure, consisting of long-chain structures of carbon particles, with controllable self-assembly to form uniformly dispersed Pt particles on their surface, and then preparing an upper proton conducting layer. Tian et al (Advanced Energy Materials, 2011, 1 (6): 1205-1214) deposited vertical carbon nanotube arrays with a length of about 1.3 μm and a diameter of less than 10 nm on the surface of aluminum foil by chemical vapor deposition and plasma enhanced chemical method, and then prepared Pt particles on the nanotube surface by physical sputtering. And hot-pressing the polymer electrolyte membrane onto a commercial polymer electrolyte membrane, removing the substrate and assembling the polymer electrolyte membrane into a single cell. At a Pt loading of 35. Mu.g/cm 2 When the power density reaches 1.03W/cm 2 It is demonstrated that better power generation performance can also be achieved at low Pt loadings.
The 3M company has commercialized third generation catalyst material-ordered membrane electrodes. Debe et al (Journal of Power Sources, 2006, 161 (2): 1002-1011; ECS Transactions, 2008, 16 (2): 1433-1442; the Electrochemical Society Transactions, 2011, 41 (1) 937-954; journal of the electrochemical society, 2012, 159 (6): K165) sputtered Pt or Pt alloys as catalyst layers by physical vapor deposition using oriented whiskers as Pt supports. Compared with the traditional Pt/C catalyst, the lath-shaped whisker formed by organic molecules (PR-149) has no carbon corrosion phenomenon, and the catalytic layer film structure formed by Pt on the whisker, rather than a single granular structure, enhances the electrochemical stability, and the ORR performance of the lath-shaped whisker can reach 5-10 times of that of common Pt nano particles. Such commercial ordered membrane electrodes have achieved the 2020 targets set forth by DOE in terms of Pt loading, specific activity, lifetime, etc. Therefore, the catalyst is a third-generation catalyst material ordered membrane electrode with high commercialization value.
Compared with the catalyst ordering membrane electrode and the support ordering membrane electrode, the proton conductor ordering membrane electrode has the following advantages: 1) The polymer electrolyte film structure without surface layer on the surface of the catalyst is more beneficial to O 2 Is transmitted by the base station; 2) Eliminating the carbon support; 3) High surface catalytic activity; 4) The tortuosity of the mass transfer path is smaller; 5) The membrane and the electrode can be made in one step; 6) The water storage performance is good. Document 1[ CN 1983684A]A method for preparing ordered membrane electrode of proton exchange membrane fuel cell is disclosed. And forming a symmetrical and ordered polymer electrolyte array membrane structure by adopting an AAO template method. Lister et al (chemElectrochem, 2015, 2, 1752-1759) prepared ordered polymer electrolyte array membrane structures using polycarbonate as a template, and then supported Pt catalysts on polymer electrolyte nanorods by PVD or CVD, and compared with the two phases, the performance of the Pt catalysts prepared by CVD was better than that prepared by PVD.
Research shows that the development of the ordered membrane electrode can effectively improve the transmission of protons, electrons and reaction gases. However, a process for preparing polymer electrolyte ordered membrane electrodes involving large-scale batch has not been reported yet.
Disclosure of Invention
In view of the problems of the prior art, the invention aims to provide a batch preparation process of an ordered large-area membrane electrode of a polymer electrolyte membrane fuel cell or an electrolytic cell. The membrane electrode prepared by the method has highly oriented and ordered proton, electron and gas mass transfer channels, effectively optimizes a three-phase reaction interface and increases the electrochemical active area of the catalyst. The method can be used for preparing the polymer electrolyte ordered membrane electrode in large scale, ensures the consistency of the performance and promotes the commercialized development of the polymer electrolyte ordered membrane electrode.
The technical scheme of the invention is as follows:
a batch preparation process of a polymer electrolyte ordered large-area membrane electrode comprises the following steps:
firstly, carrying out surface anodic oxidation by adopting a three-dimensional columnar aluminum bar to prepare a three-dimensional columnar template with porous alumina on the surface, processing a through hole in the columnar center, installing an electric heating bar or an electric heating wire, and simultaneously cleaning the processed three-dimensional columnar porous template with an array structure for later use;
step two, using the porous template treated in the step one, placing the polymer film on a reel to form a polymer film conveying belt, placing the porous template on one side or two sides of the polymer film, heating the porous template through an electric heating rod or an electric heating wire arranged in the three-dimensional columnar template, pressing the surface pattern of the porous template onto the polymer film after a certain pressure is applied, and controlling the hot pressing temperature and time to form a polymer array film structure with one side or two sides symmetrical;
step three, taking the polymer array membrane prepared in the step two as a substrate, carrying an anode catalyst on the anode side and carrying a cathode catalyst on the cathode side, so that a catalytic layer is formed on two sides of the polymer array membrane, and the preparation of a Catalyst Coated Membrane (CCM) is realized;
step four, slicing the polymer array membrane prepared in the step three and containing the cathode and anode catalytic layers to form CCM with the required size;
and fifthly, performing edge sealing treatment on the CCM obtained in the step four and the cathode and anode gas diffusion layers to prepare the required Membrane Electrode (MEA).
Specifically, as shown in fig. 1-7, the batch preparation process of the polymer electrolyte ordered membrane electrode comprises the following steps:
1) Carrying out surface anodic oxidation by adopting a three-dimensional columnar aluminum bar to prepare a three-dimensional columnar template with porous alumina on the surface, processing a through hole in the columnar center, installing an electric heating bar or an electric heating wire, and simultaneously cleaning the processed three-dimensional columnar porous template with an array structure as shown in fig. 3, and then for later use;
2) As shown in fig. 4, the three-dimensional cylindrical porous templates with electric heating rods or wires inside are placed at two sides of the conveyor belt of the polymer electrolyte membrane, the surface patterns of the templates are hot-pressed on the polymer electrolyte membrane, the temperature and time of the hot-pressing are controlled by a through pipe, so as to form a 'polymer electrolyte membrane nano rod' - 'polymer electrolyte membrane nano rod' - 'double-sided array membrane structure or' polymer electrolyte membrane nano rod '-' polymer electrolyte membrane single-sided array membrane structure '-' respectively;
3) As shown in fig. 5, the prepared polymer electrolyte array membrane is provided with an anode catalyst at the anode side and a cathode catalyst at the cathode side, so that the anode catalyst and the cathode catalyst are uniformly coated around the polymer electrolyte array rod to form a polymer electrolyte array membrane (i.e. CCM) containing the catalyst;
4) As shown in fig. 6, the prepared polymer electrolyte array membrane containing the catalytic layer is subjected to slicing treatment to form CCMs of a desired size;
5) As shown in fig. 7, the cut CCM and the gas diffusion layer are subjected to hot pressing and edge sealing treatment, and the required membrane electrode MEA is prepared.
In step 1), the porous template may be a porous metal oxide, such as alumina, or the like.
In the step 1), the pore diameter of the porous template is 50-400nm, the pore spacing is 50-250nm, and the pore depth is 0.5-2 μm.
In step 2), the thickness of the polymer electrolyte membrane is 7 to 150 μm.
In step 3), the hot pressing conditions are as follows: the temperature is 50-200 ℃ and the pressure is 0.1-50 MPa.
In step 4), the anode or cathode catalyst is a metal material having high catalytic activity, such as an electrocatalyst for oxygen reduction or oxygen evolution, such asPt、RuO 2 、IrO 2 、MnO 2 Ag and alloys or composite catalysts containing them, and electrocatalysts such as Pt, ru, ni and alloys or composite catalysts containing them for oxidation and reduction of fuel molecules.
In step 4), the catalyst preparation method comprises the following steps: the preparation can be carried out by adopting a magnetron sputtering method, a chemical vapor deposition method, an atomic layer vapor deposition method, an ultrasonic spraying method, an electrostatic spinning method and the like.
In the step 5), the size of the gas diffusion layer is consistent with that of the catalytic layer, and the hot pressing pressure is controlled to be 0.1-10MPa when the film electrode is packaged.
In the present invention, the polymer electrolyte membrane is a cation exchange membrane or an anion exchange membrane. The cation exchange membrane is a perfluorosulfonic acid membrane, a partially fluorinated sulfonic acid membrane, a non-fluorinated sulfonic acid membrane, a sulfonated polyether ether ketone membrane, a sulfonated polystyrene membrane, a sulfonated polybenzimidazole membrane, a sulfonated polyphthalimide membrane, a sulfonated polyalum membrane or a sulfonated polyether alum membrane; the anion exchange membrane is a quaternized polysulfone membrane, a quaternized polyphenylene oxide membrane and a quaternized polystyrene membrane.
Compared with the preparation technology of the membrane electrode introduced by the background technology, the method of the invention can be used for mass production of ordered large-area membrane electrodes for the fuel cell electrolytic cell, and has the following advantages: 1) The productivity of the ordered membrane electrode is improved, the size of the membrane electrode can reach more than hundred meters long and more than 1 meter wide, the production rate can reach more than 1 meter/min, and the daily productivity can reach more than 1400 square meters; 2) The batch preparation process of the invention maintains the performance consistency of the membrane electrode, and the performance deviation can be controlled to be +/-10 mV@2A/cm 2 Is within; 3) Meanwhile, the ordered membrane electrode is prepared in batches, so that the production cost of the membrane electrode can be reduced, and the processing cost of the membrane electrode can be controlled within 30 yuan/square meter; 4) The prepared membrane electrode has excellent performance, optimizes a three-phase reaction interface due to high-efficiency and ordered gas, electron and ion transmission channels, and greatly improves the electrical performance of a fuel cell and an electrolytic cell, wherein the fuel cell is arranged at the membrane electrode of 0.2mg/cm 2 The polarization performance can reach 0.65@2A/cm under the condition of the catalyst loading 2 The above.
Drawings
FIG. 1 is a flow chart of a batch preparation process of the polymer electrolyte ordered large-area membrane electrode.
Fig. 2. SEM images of the surface of the three-dimensional cylindrical porous template. Wherein, (a), (b), (c) and (d) are template photographs of different pore diameters prepared by different anodic oxidation treatments.
Fig. 3 is an exploded view and an axial sectional view of a three-dimensional cylindrical porous template having an array structure and electric heating wires.
Fig. 4 is a schematic diagram of a process for preparing a polymer electrolyte array membrane.
FIG. 5 is a schematic diagram of the preparation process of the ordered membrane electrode.
FIG. 6 is a schematic diagram of a CCM cutting process.
Fig. 7 is a schematic diagram of an mea assembly process.
Fig. 8 SEM images of polymer array membranes.
FIG. 9 is an SEM image of a catalyst-supporting polymer array membrane.
Fig. 10 is a graph of polarization performance of a proton exchange membrane fuel cell.
Detailed Description
The invention can prepare ordered membrane electrode of polymer electrolyte fuel cell or electrolytic cell in large scale, and the membrane electrode mainly comprises ion conductor, cathode and anode. The ion conductor comprises a polymer electrolyte membrane and polymer nano rods, wherein the polymer nano rods are formed by hot pressing the polymer electrolyte membrane in a porous die, namely, the polymer nano rods and the polymer electrolyte membrane are of an integrated structure, and the components are consistent.
The method for preparing the ordered membrane electrode of the polymer electrolyte fuel cell or the electrolytic cell according to the present invention, as shown in fig. 1, comprises: 1. feed (polymer electrolyte membrane); 2. rolling (polymer electrolyte array film); 3. catalytic layer preparation (catalytic layer with array features); 4. cutting into slices (catalytic layer CCM under set size); 5. hot-pressing and packaging (hot-pressing and edge sealing to prepare the membrane electrode MEA).
The materials used in the examples below were all commercial products and devices as provided in the prior art.
The invention will be further illustrated with reference to specific examples.
Example 1 application to proton exchange Membrane Fuel cells
1) Carrying out surface anodic oxidation by adopting a three-dimensional columnar aluminum rod with the length of 1 meter and the diameter of 30 cm to prepare a three-dimensional columnar template (a template with the array micropores of 400nm, the hole spacing of 250nm and the hole depth of 0.5 mu m) with porous alumina on the surface, processing a through hole with the diameter of 10 cm in the center of the aluminum rod, installing an electric heating rod or an electric heating wire with the power of 2kw, and simultaneously cleaning and drying the processed three-dimensional columnar porous template with the array structure for later use;
2) Placing a roll of Nafion film (a perfluorinated sulfonic acid film) with the width of 1 meter and the thickness of 7 mu m on a conveyor belt, allowing the Nafion film to advance along with the conveyor belt, placing the pre-cleaned porous templates on two sides of the conveyor belt, heating and pressurizing the Nafion film by the porous templates, controlling the temperature to be 120 ℃ and the pressure to be 0.1MPa, and allowing the conveyor belt to slowly advance to form a Nafion array film, wherein the microstructure of the Nafion array film is shown in figure 8;
3) Cleaning a Nafion array membrane, preparing a catalytic layer on the surface, preparing a PtCo/C catalyst on the cathode side of the membrane (the microstructure of the PtCo/C catalyst is shown in figure 9) by adopting electrostatic spinning, and preparing Pt/C on the anode side of the membrane by adopting a chemical vapor deposition method to form a CCM; the production rate can reach 1.2 meters per minute, and the daily productivity can reach 1440 square meters;
4) Cutting CCM into pieces with the length of 30 cm and the width of 10 cm, and compounding with a gas diffusion layer by hot pressing and edge sealing to form MEA; at the membrane electrode 0.2mg/cm 2 The polarization test curve of the catalyst loading of (2) is shown in FIG. 10, and the polarization performance of the fuel cell can reach 0.66@2A/cm 2 ,. The performance deviation of the membrane electrode is +/-9mV@2A/cm 2 The processing cost of the membrane electrode can be controlled at 25 yuan/square meter;
5) The fuel cell stack assembled by the MEA and the metal bipolar plate into the power of 100kW is applied to a hydrogen energy heavy truck.
Example 2 application to alkaline Fuel cells
1) The three-dimensional columnar aluminum bar with the length of 0.5 meter and the diameter of 10 cm is adopted for surface anodic oxidation to prepare the three-dimensional columnar template (the array micropores with the surface of 50nm are formed, the hole spacing is 50nm, the hole depth is 2 mu m) with the porous alumina, a through hole with the diameter of 2 cm is processed in the center of the aluminum bar, an electric heating bar or an electric heating wire with the power of 5kw is arranged, and meanwhile, the processed three-dimensional columnar porous template with the array structure is cleaned and dried for standby.
2) Placing a quaternized polysulfone membrane with the width of 0.5 m and the thickness of 15 mu m on a conveyor belt, allowing the quaternized polysulfone membrane to advance along with the conveyor belt, placing a pre-cleaned porous template on one side of the quaternized polysulfone membrane, symmetrically placing smooth stainless steel rollers (0.5 m long and 10 cm in diameter) on the other side of the quaternized polysulfone membrane, heating and pressurizing the porous template, controlling the temperature to 200 ℃ and the pressure to 50MPa, and allowing the conveyor belt to slowly advance to form an array membrane;
3) After cleaning a quaternized polysulfone array membrane, preparing a catalytic layer on the surface, preparing a nano Ag cathode catalytic layer on the array side by adopting a magnetron sputtering method, and preparing a nano Ni anode catalytic layer on the other side by adopting an ultrasonic spraying method to form CCM;
4) Cutting CCM into slices with the length of 10 cm and the width of 5 cm, and compounding with a gas diffusion layer by hot pressing and edge sealing to form MEA;
5) An alkaline fuel cell stack assembled from the MEA described above with graphite bipolar plates to a power of 5kW was used in a household power supply.
Example 3 application to Hydrogen production by Water electrolysis
1) The surface anodic oxidation is carried out by adopting a three-dimensional columnar aluminum bar with the length of 2 meters and the diameter of 50 cm, a three-dimensional columnar template (a template with the array micropores of 300 nm, the hole spacing of 150 nm and the hole depth of 1 mu m) with porous alumina on the surface is prepared, a through hole with the diameter of 8 cm is processed at the center of the aluminum bar, an electric heating bar or an electric heating wire with the power of 10kw is installed, and the processed three-dimensional columnar porous template with the array structure is simultaneously cleaned and dried for standby.
2) Placing a roll of a partially fluorinated sulfonic acid film with the width of 2 meters and the thickness of 150 mu m on a conveyor belt, allowing the roll to advance along with the conveyor belt, placing the pre-cleaned porous templates on two sides of the roll, heating and pressurizing the partially fluorinated sulfonic acid film by the porous templates, controlling the temperature to be 50 ℃ and the pressure to be 1MPa, and allowing the conveyor belt to slowly advance to form a partially fluorinated sulfonic acid array film;
3) After cleaning a part of fluorinated sulfonic acid array film, preparing a catalytic layer on the surface, and adopting an ultrasonic spraying method to treat nano IrO 2 Preparing a catalyst on the anode side (oxygen evolution) of the membrane, and preparing nano Ru on the cathode side (hydrogen evolution) of the membrane by adopting a chemical vapor deposition method to form CCM;
4) Cutting CCM into a disc shape with the diameter of 1 meter, and compounding with a gas diffusion layer by hot pressing and edge sealing to form MEA;
5) The MEA and the titanium mesh are assembled into an electrolytic tank with power of 1MW, and the electrolytic tank is applied to offshore wind power hydrogen production.
From the above embodiments, it can be seen that the method of the present invention can mass-produce the polymer electrolyte ordered large-area membrane electrode, greatly improve the production efficiency of the ordered membrane electrode, ensure the consistency of the membrane electrode, and simultaneously reduce the production cost of the membrane electrode by mass-producing the ordered membrane electrode. The prepared membrane electrode has excellent performance, optimizes a three-phase reaction interface due to high-efficiency and ordered gas, electron and ion transmission channels, and greatly improves the electrical performance of a fuel cell or an electrolytic cell, wherein the fuel cell is arranged at the membrane electrode of 0.2mg/cm 2 The polarization performance can reach 0.65@2A/cm under the condition of the catalyst loading 2 The above.
Claims (9)
1. The batch preparation process of the polymer electrolyte ordered large-area membrane electrode is characterized by comprising the following steps of:
firstly, carrying out surface anodic oxidation by adopting a three-dimensional columnar aluminum bar to prepare a three-dimensional columnar template with porous alumina on the surface, processing a through hole in the columnar center, installing an electric heating bar or an electric heating wire, and simultaneously cleaning the processed three-dimensional columnar porous template with an array structure for later use;
step two, using the three-dimensional columnar porous template treated in the step one, placing a polymer film on a reel to form a polymer film conveying belt, placing porous templates on one side or two sides of the polymer film, pressing the surface patterns of the porous templates on the polymer film after the porous templates are heated under pressure, and controlling the temperature and time of hot pressing to form a polymer array film structure with symmetrical one side or two sides;
step three, taking the polymer array membrane prepared in the step two as a substrate, carrying an anode catalyst on the anode side and carrying a cathode catalyst on the cathode side, so that a catalytic layer is formed on two sides of the polymer array membrane, and the preparation of a Catalyst Coated Membrane (CCM) is realized;
step four, slicing the polymer array membrane prepared in the step three and containing the cathode and anode catalytic layers to form CCM with the required size;
and fifthly, packaging the CCM obtained in the step four and the cathode and anode gas diffusion layers to prepare the required membrane electrode MEA.
2. The batch process of claim 1, wherein in step one, the three-dimensional cylindrical porous template is a porous metal oxide: alumina; the aperture of the three-dimensional columnar porous template is 50-400nm, the hole spacing is 50-250nm, and the hole depth is 0.5-2 mu m.
3. The batch process of claim 1, wherein in step two, the polymer film has a thickness of 7 to 150 μm.
4. A batch process according to claim 1 or 3, wherein in step two, the polymer membrane is a cation exchange membrane or an anion exchange membrane; the cation exchange membrane is a perfluorosulfonic acid membrane, a partially fluorinated sulfonic acid membrane, a non-fluorinated sulfonic acid membrane, a sulfonated polyether ether ketone membrane, a sulfonated polystyrene membrane, a sulfonated polybenzimidazole membrane, a sulfonated polyphthalimide membrane, a sulfonated polyalum membrane or a sulfonated polyether alum membrane; the anion exchange membrane is one or more than one of a quaternized alum polymer membrane, a quaternized polyphenyl ether membrane or a quaternized polystyrene membrane.
5. The batch production process according to claim 1 or 3, wherein in the second step, when the porous template is heated by using an internal electric heating rod disposed in the three-dimensional cylindrical porous template, the temperature is up to a temperature at which the polymer film can be hot-pressed to form an array, and the extrusion pressure is 0.1MPa to 50 MPa.
6. The batch production process according to claim 1, wherein in the third step, the three-dimensional columnar porous template and the polymer film can roll with each other, and the polymer film continuously travels in a transmission manner, so that the porous template continuously rolls and is hot-pressed, and the polymer array structure can be continuously produced.
7. The batch process of claim 1, wherein in step three, the catalyst is supported on the polymer electrolyte array film by magnetron sputtering, chemical vapor deposition, atomic layer vapor deposition, ultrasonic spraying, or electrospinning.
8. The batch manufacturing process of claim 1 wherein in step four CCMs of different sizes are cut as needed.
9. The batch manufacturing process of claim 1 wherein in step five, edge sealing is performed with the gas diffusion layer to form ordered membrane electrodes of different sizes as desired; the size of the gas diffusion layer is consistent with that of the catalytic layer, and when the film-forming electrode is packaged, the hot-pressing pressure is controlled to be 0.1-10MPa.
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| CN106299426A (en) * | 2016-09-22 | 2017-01-04 | 全球能源互联网研究院 | A kind of preparation technology of membrane electrode |
| CN109618561A (en) * | 2015-10-22 | 2019-04-12 | 林科闯 | Fuel cell electrode material and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109618561A (en) * | 2015-10-22 | 2019-04-12 | 林科闯 | Fuel cell electrode material and device |
| CN106299426A (en) * | 2016-09-22 | 2017-01-04 | 全球能源互联网研究院 | A kind of preparation technology of membrane electrode |
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| 机械工程手册编辑委员会等: "《电极工程手册 第44篇 检测仪表 试用本》", 机械工业出版社, pages: 298 * |
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