CN110534779B - A kind of non-fluoropolymer reinforced membrane electrode and preparation method thereof - Google Patents
A kind of non-fluoropolymer reinforced membrane electrode and preparation method thereof Download PDFInfo
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims 1
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- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- 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
- H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
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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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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Abstract
本发明涉及一种非氟聚合物增强型膜电极及其制备方法，基于非氟聚合物的增强层以及基于离子交换树脂的聚合物电解质层均以沉积形式置于气体扩散电极表面，然后组装成膜电极。本发明改变传统聚合物电解质及其增强层的存在形式，将其以溶液的形式加入到膜电极的制备过程中，最终形成一体化膜电极。这种非氟聚合物增强型膜电极及其制备方法既能避免芳香族聚合物与全氟磺酸树脂在结构不相容的问题，又能控制增强层以及聚合物电解质膜的厚度。The invention relates to a non-fluoropolymer reinforced membrane electrode and a preparation method thereof. Both a non-fluoropolymer-based reinforcement layer and an ion-exchange resin-based polymer electrolyte layer are deposited on the surface of a gas diffusion electrode, and then assembled into a membrane electrode. The present invention changes the existing form of the traditional polymer electrolyte and its reinforcing layer, and adds it in the form of a solution to the preparation process of the membrane electrode to finally form an integrated membrane electrode. The non-fluoropolymer reinforced membrane electrode and the preparation method thereof can not only avoid the structural incompatibility between the aromatic polymer and the perfluorosulfonic acid resin, but also control the thickness of the reinforced layer and the polymer electrolyte membrane.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a non-fluoropolymer reinforced membrane electrode and a preparation method thereof.
Background
A fuel cell is an electrochemical power generation device that can directly convert chemical energy of a fuel and an oxidant into electrical energy through an electrode reaction. Compared with the traditional power generation mode, the energy conversion of the fuel cell is direct, and the link of heat energy conversion is not needed, so the power generation efficiency is higher. The power generation principle is the same as that of other chemical power sources, the catalytic oxidation reaction of fuel occurs at the anode of the battery, and the catalytic reduction reaction of oxidant occurs at the cathode. The electrolyte separates the anode and the cathode and provides a proton transfer channel, and the electrons drive the load to do work through an external circuit, so that a battery load loop is formed. When the cell is in operation, fuel and oxidant are continuously fed to the cell and the electrochemical reaction is followed by the removal of reaction products and a portion of unreacted fuel and oxidant with the concomitant generation of heat.
The membrane electrode assembly is a core component of electrochemical reaction and consists of a cathode catalyst layer, an anode catalyst layer and a polymer electrolyte membrane. The membrane electrode is the main site for electrochemical reaction between fuel and oxygen, and the performance of the membrane electrode directly determines the function and efficiency of the fuel cell. One of the most directly effective ways to improve the performance of membrane electrodes today is to reduce the membrane thickness. First, a reduction in film thickness directly reduces the ohmic resistance of the fuel cell, thereby reducing ohmic polarization; secondly, the film thickness is reduced, so that the back diffusion of the water generated by the cathode is easy, and the self-humidification requirement of the membrane electrode can be met in a low-humidity environment; third, under high current operating conditions of the fuel cell, back diffusion of cathode-generated water due to reduced membrane thickness also reduces the cathode drainage pressure, thereby reducing voltage loss due to flooding. However, the reduction in film thickness has two major effects on the preparation and use of the film electrode. Firstly, the reduction of the membrane thickness makes the traditional membrane electrode preparation method difficult to implement, for example, GDE method and CCM method, and new process needs to be explored to meet the preparation of ultrathin membrane electrode; secondly, the reduction of the film thickness increases hydrogen permeation current and internal short circuit, which affects the battery life, and the introduction of the enhancement layer is needed to limit membrane swelling and reduce hydrogen permeation.
At present, fluorinated polymers, such as polytetrafluoroethylene, are mostly used as materials of the reinforcing layer of the reinforced polymer electrolyte in the membrane electrode. However, the development of fuel cells is limited by the disadvantages of high cost, low glass transition temperature and difficult processing of fluorinated polymers. Meanwhile, non-fluorine polymers, such as polyetherketone, polyethersulfone, polyimide, etc., are gradually becoming the substitute material for fluorine polymers due to the advantages of easily available raw materials, low cost, high heat-resistant temperature, etc. The main difficulties of using aromatic polymer as the material of the polymer electrolyte reinforced layer at present are: the aromatic polymer and the perfluorinated sulfonic acid resin have incompatibility in structure; due to technical problems, the ultra-thin cellular aromatic polymer reinforced layer is difficult to prepare. Therefore, a membrane electrode in which a non-fluoropolymer is used as a reinforcing layer has not been used.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a non-fluorine polymer reinforced membrane electrode and a preparation method thereof, which are a novel membrane electrode preparation technology, changes the existing form of the traditional polymer electrolyte and the reinforced layer thereof, and adds the traditional polymer electrolyte and the reinforced layer thereof into the preparation process of the membrane electrode in the form of solution to finally form an integrated membrane electrode. The non-fluorine polymer reinforced membrane electrode and the preparation method thereof can not only avoid the problem of structural incompatibility of aromatic polymer and perfluorinated sulfonic acid resin, but also control the thickness of the reinforced layer and the polymer electrolyte membrane. At present, no relevant literature report of the membrane electrode is available.
The invention adopts the following technical scheme that a non-fluorine polymer reinforced membrane electrode, a non-fluorine polymer based reinforced layer and an ion exchange resin based polymer electrolyte layer are arranged on the surface of a gas diffusion electrode in a deposition mode and then assembled into the membrane electrode. The material and the material of the reinforcing layer are wide in selection range, and the thicknesses of the reinforcing layer and the polymer electrolyte layer are accurate and controllable.
In a preferred embodiment of the present invention, the material of the reinforcing layer is a non-fluorine polymer material, and includes one or more of polyethersulfone polymer, polyetherketone polymer, polyimide polymer, polynorbornene polymer, polyolefin polymer, polycarbonate polymer, polyarylethernitrile, and polyaryletherphosphine oxide; the ion exchange resin comprises anion exchange resin and cation exchange resin; the anion exchange resin comprises one or more of perfluoro anionic polymers, polyarylether anionic polymers, polyolefin anionic polymers, polyaryl ketone anionic polymers and polynorbornene anionic polymers; the cation exchange resin comprises one or more of perfluorosulfonic acid polymers, sulfonated polyarylether polymers, sulfonated polyolefin polymers, sulfonated polyaryl ketone polymers and sulfonated polynorbornene.
In a preferred embodiment of the invention, the reinforcement layer material is deposited in the form of electrospinning on the surface of the gas diffusion electrode; and depositing the solution of the ion exchange resin on the enhancement layer by one of spraying, transfer printing, chemical deposition, electrochemical deposition, physical sputtering deposition, dry powder spraying and printing, and then assembling into the membrane electrode.
In a preferred embodiment of the present invention, the method for preparing the non-fluoropolymer reinforced membrane electrode comprises the following specific steps:
(1) adding a catalyst into deionized water, uniformly stirring, adding a solvent for dilution, and performing ultrasonic dispersion in an ice-water bath to obtain a catalyst solution;
(2) adding ion exchange resin into the catalyst solution in the step (1), and performing ultrasonic dispersion to prepare catalyst slurry;
(3) depositing the catalyst slurry obtained in the step (2) on the surface of the gas diffusion layer;
(4) depositing a non-fluoropolymer solution on the surface of the double-layer gas diffusion electrode obtained in the step (3) by an electrostatic spinning technology;
(5) depositing a solution of ion exchange resin on the electrospun fiber obtained in the step (4);
(6) and (5) carrying out hot pressing on the half cell obtained in the step (5) to obtain the membrane electrode.
In a preferred embodiment of the present invention, in the step (1), the catalyst includes a platinum-based catalyst, an alloy-based catalyst and a non-noble metal catalyst.
In a preferred embodiment of the present invention, in step (1), the solvent is an alcohol compound; the alcohol compound comprises one or more of methanol, ethanol, ethylene glycol, n-propanol and isopropanol.
In a preferred embodiment of the present invention, in step (1), the catalyst solution comprises 7-8 parts of catalyst, 100-500 parts of deionized water, and 5000-10000 parts of alcohol compound.
In a preferred embodiment of the present invention, in the step (1), the ion exchange resin comprises an anion exchange resin and a cation exchange resin; the anion exchange resin comprises one or more of perfluoro anionic polymers, polyarylether anionic polymers, polyolefin anionic polymers, polyarone anionic polymers and polynorbornene anionic polymers; the cation exchange resin comprises one or more of perfluorosulfonic acid polymers, sulfonated polyarylether polymers, sulfonated polyolefin polymers, sulfonated polyaryl ketone polymers and sulfonated polynorbornene.
In a preferred embodiment of the present invention, in the step (1), the stirring time is 10 to 200 minutes; the time of ultrasonic dispersion is 10-200 minutes.
In a preferred embodiment of the invention, the mass ratio of the catalyst to the ion exchange resin is 3-4: 1.
In a preferred embodiment of the present invention, in the step (2), the time for the ultrasonic dispersion is 10 to 200 minutes.
In a preferred embodiment of the present invention, in the step (3), the deposition method includes one of spraying, transfer printing, chemical deposition, electrochemical deposition, physical sputtering deposition, dry powder spraying, and printing.
In a preferred embodiment of the present invention, in step (4), the non-fluorine polymer includes one or more of polyethersulfone polymer, polyetherketone polymer, polyimide polymer, polynorbornene polymer, polyolefin polymer, polycarbonate polymer, polyarylethernitrile, and polyaryletherphosphine oxide.
In a preferred embodiment of the present invention, in step (4), the electrospinning parameters include a solution concentration of 3 to 35wt.% and a spinning time of 0.5 to 10 minutes.
In a preferred embodiment of the present invention, in the step (5), the ionic polymer comprises an anion exchange resin and a cation exchange resin; the anion exchange resin comprises one or more of perfluoro anionic polymers, polyarylether anionic polymers, polyolefin anionic polymers, polyarone anionic polymers and polynorbornene anionic polymers; the cation exchange resin comprises one or more of perfluorosulfonic acid polymers, sulfonated polyarylether polymers, sulfonated polyolefin polymers, sulfonated polyaryl ketone polymers and sulfonated polynorbornene.
In a preferred embodiment of the present invention, in the step (5), the deposition method includes one of spraying, transfer printing, chemical deposition, electrochemical deposition, physical sputtering deposition, dry powder spraying, and printing.
In a preferred embodiment of the present invention, in the step (6), the hot pressing time is 1 to 10 minutes, and the hot pressing temperature is 80 to 160 minutesoC。
Compared with the traditional membrane electrode, the invention has the following beneficial effects:
1. the membrane electrode prepared by the invention has double layers of enhancement layers, so that the hydrogen permeation current density of the membrane electrode can be effectively reduced, the performance of the membrane electrode is improved, and the service life of the membrane electrode is prolonged.
2. In the membrane electrode prepared by the invention, the types of the reinforcing layer materials and the polymer electrolyte materials can be selected in a wide range, and the thickness of the reinforcing layer and the thickness of the polymer electrolyte layer are accurate and controllable.
3. The preparation process of the invention has simple process, safety, environmental protection and low cost, saves the production process of the reinforcement and the membrane material, and can be popularized and applied.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a schematic sectional view and a scanning electron microscope image of the film electrode of example 1. The polyether sulfone fiber layer is clearly visible and is close to one side of the catalyst layer, so that the polyether sulfone fiber layer has a reinforcing effect on the polymer electrolyte layer.
FIG. 2 shows the polarization curve, high frequency resistance and power density of the membrane electrode of example 1. In the figure, the self-made membrane electrode is the membrane electrode prepared by the invention (example 1), and the conventional membrane electrode is the membrane electrode prepared by a CCM method based on a Nafion 211 membrane.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
Example 1
1. Preparing a catalytic layer slurry based on perfluorosulfonic acid resin:
preparing catalyst layer slurry according to the mass ratio of 7 parts of Pt/C catalyst, 3 parts of perfluorinated sulfonic acid resin, 100 parts of deionized water and 5000 parts of solvent, wherein the perfluorinated sulfonic acid resin is Nafion resin, and the solvent is ethanol.
2. Preparation of gas diffusion electrodes
The catalyst slurry was ultrasonically sprayed onto the surface of the gas diffusion layer. By controlling the spraying time, the catalyst loading capacity of the gas diffusion electrode is controlled to be 0.2 mg/cm respectively2(Anode) and 0.4mg/cm2(cathode).
3. Preparation of polyethersulfone reinforcement layer
And (3) electrostatic spinning the polyether sulfone polymer on the surface of the gas diffusion electrode. The concentration of the polyether sulfone solution is 15%, and the solvent is a mixed solvent of N, N-dimethylformamide and acetone; the electrospinning time was 2 minutes.
4. Preparation of Polymer electrolyte layer
The perfluorosulfonic acid resin solution was ultrasonically sprayed onto the electrospun layer. Controlling the net loading of the resin at 2.0mg/cm by controlling the spraying time2。
5. Membrane electrode hot pressing
Hot-pressing the obtained cathode and anode half cell to obtain a membrane electrode, wherein the hot-pressing time is 3 minutes, and the hot-pressing temperature is 140 DEGoC。
6. Single cell assembly and testing
The prepared membrane electrode is assembled into a single cell, and the effective reaction area is 5cm2；
The test conditions for the polarization curve were: hydrogen/oxygen, back pressure 2.5bar, cell temperature 80 ℃, cathode and anode relative humidity 30%, gas excess coefficient: anode 1.25, cathode 2.0; performed using test standards for U.S. DOE.
The test result is shown in fig. 2, under the same test conditions, the membrane electrode prepared by the technology of the invention has better performance than the membrane electrode prepared by the traditional CCM method, and the internal resistance of the cell is lower.
Example 2
1. Preparing catalytic layer slurry based on sulfonated polyether sulfone resin:
preparing catalyst layer slurry according to the mass ratio of 7 parts of Pt/C catalyst, 3 parts of sulfonic acid resin, 100 parts of deionized water and 5000 parts of solvent, wherein the perfluorinated sulfonic acid resin is sulfonated polyether sulfone resin, and the solvent is ethanol.
2. Preparation of gas diffusion electrodes
The catalyst slurry was ultrasonically sprayed onto the surface of the gas diffusion layer. By controlling the spraying time, the catalyst loading capacity of the gas diffusion electrode is controlled to be 0.2 mg/cm respectively2(Anode) and 0.4mg/cm2(cathode)。
3. Preparation of polyethersulfone reinforcement layer
And (3) electrostatic spinning the polyether sulfone polymer on the surface of the gas diffusion electrode. The concentration of the polyether sulfone solution is 15%, and the solvent is a mixed solvent of N, N-dimethylformamide and acetone; the electrospinning time was 2 minutes.
4. Preparation of Polymer electrolyte layer
And ultrasonically spraying the sulfonated polyether sulfone resin solution on the electrostatic spinning layer. Controlling the net loading of the resin at 2.0mg/cm by controlling the spraying time2。
5. Membrane electrode hot pressing
Hot-pressing the obtained cathode and anode half cell to obtain a membrane electrode, wherein the hot-pressing time is 3 minutes, and the hot-pressing temperature is 140 DEGoC。
6. Single cell assembly and testing
The prepared membrane electrode is assembled into a single cell, and the effective reaction area is 5cm2；
The test conditions for the polarization curve were: hydrogen/oxygen, back pressure 2.5bar, cell temperature 80 ℃, cathode and anode relative humidity 30%, gas excess coefficient: anode 1.25, cathode 2.0; performed using test standards for U.S. DOE.
Example 3
1. Preparing catalytic layer slurry based on basic anion exchange resin:
preparing catalytic layer slurry according to the mass ratio of 7 parts of Pt/C catalyst, 3 parts of anion exchange resin, 100 parts of deionized water and 5000 parts of solvent, wherein the anion exchange resin is FuMA-Tech anion exchange resin, and the solvent is ethanol.
2. Preparation of gas diffusion electrodes
The catalyst slurry was ultrasonically sprayed onto the surface of the gas diffusion layer. By controlling the spraying time, the catalyst loading capacity of the gas diffusion electrode is controlled to be 0.2 mg/cm respectively2(Anode) and 0.4mg/cm2(cathode).
3. Preparation of polyethersulfone reinforcement layer
And (3) electrostatic spinning the polyether sulfone polymer on the surface of the gas diffusion electrode. The concentration of the polyether sulfone solution is 15%, and the solvent is a mixed solvent of N, N-dimethylformamide and acetone; the electrospinning time was 2 minutes.
4. Preparation of Polymer electrolyte layer
The solution of Fuma-tech anion exchange resin was sprayed ultrasonically onto the electrospun layer. Controlling the net loading of the resin at 2.0mg/cm by controlling the spraying time2。
5. Membrane electrode hot pressing
Hot-pressing the obtained cathode and anode half cell to obtain a membrane electrode, wherein the hot-pressing time is 3 minutes, and the hot-pressing temperature is 100 DEGoC。
6. Single cell assembly and testing
The prepared membrane electrode is assembled into a single cell, and the effective reaction area is 5cm2；
The test conditions for the polarization curve were: hydrogen/oxygen, back pressure 2.5bar, cell temperature 80 ℃, cathode and anode relative humidity 30%, gas excess coefficient: anode 1.25, cathode 2.0; performed using test standards for U.S. DOE.
Example 4
1. Preparing catalyst layer slurry based on quaternary ammonium salt type polyether sulfone resin:
preparing catalyst layer slurry according to the mass ratio of 7 parts of Pt/C catalyst, 3 parts of anion exchange resin, 100 parts of deionized water and 5000 parts of solvent, wherein the anion exchange resin is quaternary ammonium salt type polyether sulfone resin, and the solvent is ethanol.
2. Preparation of gas diffusion electrodes
The catalyst slurry was ultrasonically sprayed onto the surface of the gas diffusion layer. By controlling the spraying time, the catalyst loading capacity of the gas diffusion electrode is controlled to be 0.2 mg/cm respectively2(Anode) and 0.4mg/cm2(cathode).
3. Preparation of the reinforcing layer
And (3) electrostatic spinning the polyether sulfone polymer on the surface of the gas diffusion electrode. The concentration of the polyether sulfone solution is 15%, and the solvent is a mixed solvent of N, N-dimethylformamide and acetone; the electrospinning time was 2 minutes.
4. Preparation of Polymer electrolyte layer
And ultrasonically spraying the quaternary ammonium salt type polyether sulfone resin solution on the electrostatic spinning layer. Controlling the net loading of the resin at 2.0mg/cm by controlling the spraying time2。
5. Membrane electrode hot pressing
Hot-pressing the obtained cathode and anode half cell to obtain a membrane electrode, wherein the hot-pressing time is 3 minutes, and the hot-pressing temperature is 100 DEGoC。
6. Single cell assembly and testing
The prepared membrane electrode is assembled into a single cell, and the effective reaction area is 5cm2；
The test conditions for the polarization curve were: hydrogen/oxygen, back pressure 2.5bar, cell temperature 80 ℃, cathode and anode relative humidity 30%, gas excess coefficient: anode 1.25, cathode 2.0; performed using test standards for U.S. DOE.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
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