CN112736271B - Composite proton exchange membrane based on acetate fiber porous support body and preparation method thereof - Google Patents
Composite proton exchange membrane based on acetate fiber porous support body and preparation method thereof Download PDFInfo
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1053—Polymer electrolyte composites, mixtures or blends consisting of layers of polymers with at least one layer being ionically conductive
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
- H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
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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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
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- 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
The invention discloses a composite proton exchange membrane based on an acetate fiber porous support body and a preparation method thereof. The preparation method comprises the steps of coating the membrane casting solution on the porous acetate fiber support body by adopting a preset coating process, drying the porous acetate fiber support body by using a first drying oven, spraying the crosslinking agent and the inorganic oxide solution by adopting a preset spraying process, rolling the porous acetate fiber support body by using a hot-pressing composite roller to carry out leveling and crosslinking reaction, and drying the porous acetate fiber support body by using a second drying oven to obtain the composite proton exchange membrane based on the porous acetate fiber support body. The proton exchange composite membrane prepared by the invention has high proton conductivity, high mechanical strength, compactness and high uniformity.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to a composite proton exchange membrane based on an acetate fiber porous support body and a preparation method thereof.
Background
Fuel cells are considered to be the first clean and efficient power generation technology in the 21 st century, and are the most effective and promising field for solving energy problems. Among them, the proton exchange membrane fuel cell is receiving attention due to its advantages of green, high efficiency and simple structure. Proton exchange membranes are one of the core components of membrane fuel cells. Proton conductivity is a core parameter of proton exchange membranes and determines cell performance. The electrolyte plays the roles of guiding protons, blocking electrons and separating reactants in the battery, and the performance and the service life of the battery are directly determined by the performance of the electrolyte. The ideal proton exchange membrane should have high proton conductivity, good alcohol-blocking performance, good chemical and thermal stability, and low cost and easy availability. The currently commercialized proton exchange membrane is a perfluorosulfonic acid membrane represented by Nafion, which has high proton conductivity at normal temperature and saturated humidity, but under ideal operating conditions, when the temperature is higher than 100 ℃ and the relative humidity is lower than 50%, the membrane rapidly loses water, so that the proton conductivity is sharply reduced. In addition, the perfluorosulfonic acid membrane is expensive and has serious methanol permeation, and the factors seriously restrict the application of the perfluorosulfonic acid membrane in the field of proton exchange membrane fuel cells.
In order to overcome the defects of the Nafion membrane, researchers mainly study composite membranes, and on the one hand, the relatively common preparation of the composite membranes mainly uses an expanded Polytetrafluoroethylene (PTFE) microporous membrane as a support body to prepare a proton exchange membrane by impregnation. The Polytetrafluoroethylene (PTFE) porous membrane is used as a support because of strong mechanical strength, size and chemical stability, and the perfluorinated sulfonic acid resin is directly cast into the pores to prepare the composite membrane, so that the consumption of the perfluorinated sulfonic acid resin is reduced, the thickness of the membrane can be reduced, and the cost of the proton exchange membrane and the internal resistance of the cell are reduced. However, since the porous polytetrafluoroethylene membrane has a large surface tension, the surface of the porous polytetrafluoroethylene membrane is usually modified with an acid or a base, or a surfactant, a high-boiling solvent, or even a high-voltage electric field is applied to increase the filling amount and distribution uniformity of the perfluorosulfonic acid resin, so as to obtain a high-performance composite membrane. The method increases the preparation process of the composite membrane, and isopropanol easily dissolves the resin, so that the resin is lost and the compactness of the membrane is damaged.
On the other hand, the sulfonated aromatic polymer is expected to be a substitute material for perfluorosulfonic acid membranes because of its excellent mechanical properties, outstanding heat resistance, chemical stability and low fuel permeability. However, the rigid aromatic polymer backbone structure hinders the formation of a continuous hydrophilic-hydrophobic phase separation structure, so that the proton conductivity of the aromatic polymer membrane is lower than that of the perfluorosulfonic acid membrane. Increasing the degree of sulfonation is one of the effective means to enhance proton conductivity of aromatic polymer membranes. However, higher sulfonation also often results in a significant increase in water absorption of the polymer membrane, which can result in a decrease in the dimensional stability, alcohol barrier properties, and mechanical properties of the membrane, thereby affecting the practical use of high sulfonation polymer membranes. The composite membrane cannot completely solve the preparation defects of the proton exchange membrane and the running performance in a high-temperature low-humidity environment.
Disclosure of Invention
The invention aims to provide a preparation method of a composite proton exchange membrane based on an acetate fiber porous support body, which aims to solve the problem of wettability of the support body and a polymer in the preparation process of a composite membrane and improve the battery performance of the proton exchange membrane in a high-temperature low-humidity environment.
The technical means adopted by the invention are as follows:
a composite proton exchange membrane based on an acetate fiber porous support body is prepared from the acetate fiber porous support body, a polymer proton conductor, an additive for enhancing proton conduction, an inorganic oxide and a cross-linking agent;
the polymer proton conductor is any one of sulfonated polyether ether ketone, sulfonated polyether sulfone and sulfonated polyphenylsulfone; the proton conduction enhancing additive is one or a combination of more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, zirconium hydrogen phosphate and cerium hydrogen phosphate; the inorganic oxide is any one of nano zinc oxide and nano silicon dioxide; the cross-linking agent is any one of dicumyl peroxide and benzoyl peroxide; the mass ratio of the polymer proton conductor to the proton conduction enhancing additive to the inorganic oxide to the cross-linking agent is 1:0.1-0.15:0.05-0.15: 0.025-0.15.
The invention also provides a preparation method of the composite proton exchange membrane based on the cellulose acetate porous support body, which comprises the following steps:
(1) dissolving a polymer proton conductor in a solvent, and stirring at room temperature to obtain a polymer proton conductor solution with the concentration of 5-15 wt%; the solvent is a mixed solvent of a compound A, deionized water and isopropanol, and the mass ratio of the compound A to the deionized water to the isopropanol is 10:5: 4; the compound A is any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpyrrolidone or dimethyl sulfoxide;
(2) adding the proton conduction enhancing additive into the polymer proton conductor solution, and standing and defoaming to obtain a membrane casting solution;
(3) weighing a cross-linking agent and an inorganic oxide, dispersing the cross-linking agent and the inorganic oxide in a mixed solvent of deionized water and ethanol, and preparing a cross-linking agent and inorganic oxide mixed solution with the total concentration of 0.1-0.9 wt%; the mass ratio of the deionized water to the ethanol is 1: 0.5-1;
(4) and coating the casting solution on the porous acetate fiber support body by adopting a preset coating process, drying by using a first oven, spraying a cross-linking agent and inorganic oxide mixed solution by adopting a preset spraying process, rolling by using a hot-pressing composite roller, and drying by using a second oven to obtain the composite proton exchange membrane based on the porous acetate fiber support body.
The polymer proton conductor is any one of sulfonated polyether ether ketone, sulfonated polyether sulfone or sulfonated polyphenylsulfone; the proton conduction enhancing additive is one or a combination of more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, zirconium hydrogen phosphate or cerium hydrogen phosphate.
Further, in the step (2), the mass of the proton conduction enhancing additive is 5-15% of the mass of the polymer proton conductor.
Further, in the step (3), the cross-linking agent is any one of dicumyl peroxide and benzoyl peroxide; the inorganic oxide is any one of nano zinc oxide and nano silicon dioxide.
Further, in the step (3), the mass ratio of the crosslinking agent to the inorganic oxide is 1: 0.1-1.
Further, in the step (4), the coating speed is 1-5m/min, and the coating thickness (wet thickness) is 20-50 μm; the spraying flow rate is 5-10mL/min, and the spraying speed is 100-300 mm/s.
Further, in the step (4), the coating and drying temperature is 60-100 ℃; the spraying and drying temperature is 150-200 ℃; the rolling pressure is 1-15MPa, and the rolling temperature is 120-200 ℃.
The preparation method adopts continuous coating equipment, wherein a coating die head, a first drying oven, a spraying chamber, a pair of mutually meshed hot-pressing composite rollers, a second drying oven and a wind-up roller are sequentially arranged in the continuous coating equipment along the conveying direction of the composite proton exchange membrane; a spray head is arranged in the spraying chamber; the production equipment also comprises a plurality of conveying rollers for conveying the composite proton exchange membrane forwards.
The invention also provides a composite proton exchange membrane obtained by the preparation method.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the acetate fiber porous support body as the base membrane to prepare the proton exchange composite membrane, and the acetate fiber porous support body has the advantages of high selectivity, high mechanical strength, good hydrophilicity, low price and the like. Due to excellent hydrophilicity, the cellulose acetate porous polymer proton conductor has better compatibility, the phenomena of falling off of the polymer proton conductor and the like caused by small surface tension are avoided, and the prepared composite membrane has the advantage of high stripping resistance; the active layer of the prepared proton exchange composite membrane is ultrathin, compact and free of defects.
2. The heteropoly acid compound with proton conductivity is added into the casting solution, so that the proton conductivity of the composite membrane is further improved, and the heteropoly acid interacts with a polymer proton conductor with nitrogen heterocycle in the volatilization process of an organic solvent, so that the heteropoly acid is prevented from losing on the basis of improving the performance of a fuel cell.
3. According to the invention, after the membrane casting solution is coated on the porous acetate fiber support, the mixed solution with the cross-linking agent and the inorganic oxide is sprayed on the porous acetate fiber support, and the heat cross-linking reaction is carried out through hot-pressing composite rolling, wherein the cross-linking agent and the inorganic oxide are interacted, so that the mechanical strength and the aging resistance of the proton exchange composite membrane are improved, the moisture-preserving capability of the proton exchange membrane is improved through the inorganic oxide, and the operation of the fuel cell in a high-temperature low-humidity environment is still not influenced.
4. The preparation process is simple and quick, is suitable for large-scale batch production, and can reduce larger pores in the composite membrane by adding the cross-linking agent, so that the prepared composite membrane is compact and high in uniformity.
Drawings
In order to more clearly illustrate the embodiments of the present invention 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 introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing a composite proton exchange membrane according to the present invention.
In the figure: 1. a cellulose acetate porous support; 2. a coating die head; 3. casting solution; 4-1, drying in a first oven; 4-2, and a second oven; 5. a spray chamber; 5-1, a spray head; 6. hot-pressing a composite roller; 7. a proton exchange composite membrane; 8. and (7) winding the roller.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The cellulose acetate porous support is a cellulose acetate membrane which is directly commercially available and used as a support.
Example 1
(1) Weighing 10g of sulfonated polyether ether ketone, adding the sulfonated polyether ether ketone into a mixed solvent of 100g N-methyl pyrrolidone, 50g of isopropanol and 40g of deionized water, and stirring for 12 hours at room temperature to obtain a polymer transparent solution with the concentration of 5 wt%;
(2) weighing 0.25g of phosphotungstic acid, adding the phosphotungstic acid into the transparent polymer solution in the step (1), stirring for 1 hour at room temperature, and standing and defoaming to obtain a membrane casting solution 3;
(3) weighing 1g of dicumyl peroxide and 0.1g of nano silicon dioxide, adding the weighed materials into a mixed solvent of 666g of deionized water and 333g of ethanol, and ultrasonically dispersing the materials uniformly for later use;
(4) uniformly coating the casting solution 3 in the step (2) on a cellulose acetate porous support 1 by a coating die head 2 for a coating process with the coating speed of 1m/min and the coating thickness of 20 mu m, drying in a 60 ℃ oven I4-1, then spraying the dispersion in the step (3) on the cellulose acetate porous support 1 coated with the casting solution 3 in a spraying chamber 5 by a spraying process with the spraying flow rate of 5mL/min and the spraying moving speed of a nozzle 5-1 of 100mm/s, rolling by a hot-pressing composite roller 6 with the pressure of 1MPa and the temperature of 120 ℃ to enable the cross-linking agent and the nano silicon dioxide to interact and be thermally cross-linked with the polymer to obtain a proton exchange composite membrane 7, and finally drying in a 150 ℃ oven II 4-2 and rolling by a rolling roller 8.
Example 2
(1) Weighing 20g of sulfonated polyether sulfone, adding the sulfonated polyether sulfone into a mixed solvent of 59g N, N-dimethylformamide, 30g of isopropanol and 24g of deionized water, and stirring at room temperature for 12 hours to obtain a polymer transparent solution with the concentration of 15 wt%;
(2) weighing 3g of phosphomolybdic acid, adding the phosphomolybdic acid into the transparent polymer solution in the step (1), stirring for 1 hour at room temperature, and standing and defoaming to obtain a membrane casting solution 3;
(3) weighing 3g of benzoyl peroxide and 3g of nano zinc oxide, adding the benzoyl peroxide and the nano zinc oxide into a mixed solvent of 333g of deionized water and 333g of ethanol, and ultrasonically dispersing the mixture uniformly for later use;
(4) uniformly coating the casting solution 3 in the step (2) on a cellulose acetate porous support 1 by a coating die head 2 for a coating process with the coating speed of 5m/min and the coating thickness of 50 mu m, drying in a drying oven I4-1 at the temperature of 100 ℃, then spraying the dispersion in the step (3) on the cellulose acetate porous support 1 coated with the casting solution 3 in a spraying chamber 5 by a spraying process with the spraying flow rate of 10mL/min and the spraying moving speed of a spray head 5-1 of 300mm/s, rolling by a hot-pressing composite roller 6 with the pressure of 15MPa and the temperature of 200 ℃ to enable the cross-linking agent and the nano zinc oxide to mutually react and be thermally cross-linked with the polymer to obtain a proton exchange composite membrane 7, and finally drying in a drying oven II 4-2 at the temperature of 200 ℃ and rolling by a rolling roller 8.
Example 3
(1) Weighing 20g of sulfonated polyphenylsulfone, adding the sulfonated polyphenylsulfone into a mixed solvent of 95g of dimethyl sulfoxide, 47g of isopropanol and 38g of deionized water, and stirring at room temperature for 12 hours to obtain a polymer transparent solution with the concentration of 10 wt%;
(2) weighing 2g of silicotungstic acid, adding the silicotungstic acid into the polymer transparent solution in the step (1), stirring for 1 hour at room temperature, and standing and defoaming to obtain a membrane casting solution 3;
(3) weighing 1g of benzoyl peroxide and 0.5g of nano silicon dioxide, adding the benzoyl peroxide and the nano silicon dioxide into a mixed solvent of 165g of deionized water and 133g of ethanol, and uniformly dispersing by ultrasonic for later use;
(4) uniformly coating the casting solution 3 in the step (2) on a porous acetate fiber support 1 by using a coating die head 2 in a coating process with the coating speed of 3m/min and the coating thickness of 30 mu m, drying the porous acetate fiber support 1 in an oven I4-1 at the temperature of 80 ℃, then spraying the dispersion solution in the step (3) on the porous acetate fiber support 1 coated with the casting solution 3 in a spraying chamber 5 by using a spraying process with the spraying flow rate of 80mL/min and the spraying moving speed of a sprayer 5-1 of 200mm/s, rolling the porous acetate fiber support by using a hot-pressing composite roller 6 with the pressure of 10MPa and the temperature of 180 ℃ to enable a cross-linking agent and nano zinc oxide to interact and be thermally cross-linked with a polymer to obtain a proton exchange composite membrane 7, and finally drying the porous acetate fiber support in an oven II 4-2 at the temperature of 150 ℃ and rolling the porous acetate fiber support by using a rolling roller 8.
Comparative example 1
(1) Weighing 20g of sulfonated polyphenylsulfone, adding the sulfonated polyphenylsulfone into a mixed solvent of 95g of dimethyl sulfoxide, 47g of isopropanol and 38g of deionized water, and stirring at room temperature for 12 hours to obtain a polymer transparent solution with the concentration of 10 wt%;
(2) weighing 2g of silicotungstic acid, adding the silicotungstic acid into the polymer transparent solution in the step (1), stirring for 1 hour at room temperature, and standing and defoaming to obtain a membrane casting solution 3;
(3) and (3) uniformly coating the casting solution 3 in the step (2) on the cellulose acetate porous support 1 by using a coating die head 2 in a coating process with the coating speed of 3m/min and the coating thickness of 30 mu m, drying in a first drying oven 4-1 at the temperature of 80 ℃, drying in a second drying oven 4-2 at the temperature of 150 ℃ to obtain a proton exchange composite membrane 7, and winding by using a winding roller 8.
Comparative example 2
(1) Weighing 20g of sulfonated polyether sulfone, adding the sulfonated polyether sulfone into a mixed solvent of 59g N, N-dimethylformamide, 30g of isopropanol and 24g of deionized water, and stirring at room temperature for 12 hours to obtain a polymer transparent solution with the concentration of 15 wt%;
(2) weighing 3g of benzoyl peroxide and 3g of nano zinc oxide, adding into a mixed solvent of 333g of deionized water and 333g of ethanol, and uniformly dispersing by ultrasonic for later use;
(3) uniformly coating the casting solution 3 in the step (2) on a cellulose acetate porous support 1 by a coating die head 2 for a coating process with the coating speed of 5m/min and the coating thickness of 50 mu m, drying in a drying oven I4-1 at the temperature of 100 ℃, then spraying the dispersion in the step (3) on the cellulose acetate porous support 1 coated with the casting solution 3 in a spraying chamber 5 by a spraying process with the spraying flow rate of 10mL/min and the spraying moving speed of a spray head 5-1 of 300mm/s, rolling by a hot-pressing composite roller 6 with the pressure of 15MPa and the temperature of 200 ℃ to enable the cross-linking agent and the nano zinc oxide to mutually react and be thermally cross-linked with the polymer to obtain a proton exchange composite membrane 7, and finally drying in a drying oven II 4-2 at the temperature of 200 ℃ and rolling by a rolling roller 8.
Comparative example 3
(1) Weighing 20g of sulfonated polyether sulfone, adding the sulfonated polyether sulfone into a mixed solvent of 59g N, N-dimethylformamide, 30g of isopropanol and 24g of deionized water, and stirring at room temperature for 12 hours to obtain a polymer transparent solution with the concentration of 15 wt%;
(2) weighing 3g of benzoyl peroxide and 3g of nano zinc oxide, adding the benzoyl peroxide and the nano zinc oxide into a mixed solvent of 333g of deionized water and 333g of ethanol, and ultrasonically dispersing the mixture uniformly for later use;
(3) uniformly coating the casting solution 3 in the step (2) on a polytetrafluoroethylene microporous membrane by using a coating die head 2 in a coating process with the coating speed of 5m/min and the coating thickness of 50 mu m, drying the polytetrafluoroethylene microporous membrane in a drying oven I4-1 at the temperature of 100 ℃, then spraying the dispersion solution in the step (3) on the polytetrafluoroethylene microporous membrane coated with the casting solution 3 in a spraying chamber 5 in a spraying process with the spraying flow rate of 10mL/min and the spraying moving speed of a spray head 5-1 of 300mm/s, rolling the polytetrafluoroethylene microporous membrane by using a hot-pressing composite roller 6 with the pressure of 15MPa and the temperature of 200 ℃ to enable a cross-linking agent and nano zinc oxide to mutually react and be thermally linked with a polymer to obtain a proton exchange composite membrane 7, and finally drying the proton exchange composite membrane in an drying oven II 4-2 at the temperature of 200 ℃ and rolling the proton exchange composite membrane by using a rolling roller 8.
Test example
The proton exchange composite membranes prepared in examples 1 to 3 and comparative examples 1 to 3 were tested for electrical conductivity, tensile strength, hydrogen permeation current, and dimensional change rate. Wherein the conductivity test conditions are as follows: the test method of the tensile strength at 105 ℃, 50% humidity and 40 ℃ and 80% humidity is the national standard method (GB/T20042.3-2009); the test method of the hydrogen permeation current is an electrochemical method. The results of the measurements are shown in the following table:
in the examples 1 to 3, the proton exchange composite membranes with different thicknesses are prepared by controlling the polymer contents of different membrane casting solutions, and all the proton exchange composite membranes show higher proton conductivity in the operation process of the fuel cell, and the attenuation of the proton conductivity is very small along with the gradual rise of the operation temperature to 105 ℃, so that the proton exchange composite membranes prepared after the cross-linking reaction have high mechanical strength and good dimensional stability.
In comparative example 1, the proton exchange composite membrane prepared without spraying a cross-linking agent and performing a thermal cross-linking reaction has lower mechanical strength; in comparative example 2, no additive capable of increasing proton conductivity was added to the casting solution, and the proton conductivity was significantly low. The comparative example 3 does not use an acetate fiber porous support, adopts a common polytetrafluoroethylene microporous membrane, has smaller surface tension and strong hydrophobicity, and proton conductor resin cannot be in better contact with the polytetrafluoroethylene microporous membrane, so that the prepared composite membrane has pinholes, and the electrochemical performance and the mechanical performance of the composite membrane are poorer.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a composite proton exchange membrane based on an acetate fiber porous support body is characterized by comprising the following steps:
(1) dissolving a polymer proton conductor in a solvent, and stirring at room temperature to obtain a polymer proton conductor solution with the concentration of 5-15 wt%; the polymer proton conductor is any one of sulfonated polyether ether ketone, sulfonated polyether sulfone or sulfonated polyphenylsulfone; the solvent is a mixed solvent of a compound A, deionized water and isopropanol, and the mass ratio of the compound A to the deionized water to the isopropanol is 10:5: 4; the compound A is any one of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylpyrrolidone or dimethyl sulfoxide;
(2) adding the proton conduction enhancing additive into the polymer proton conductor solution, and standing and defoaming to obtain a membrane casting solution; the proton conduction enhancing additive is one or a combination of more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, zirconium hydrogen phosphate or cerium hydrogen phosphate;
(3) weighing a cross-linking agent and an inorganic oxide, and dispersing in a mixed solvent to prepare a cross-linking agent and inorganic oxide mixed solution; the mixed solvent comprises deionized water and ethanol, and the mass ratio of the deionized water to the ethanol is 1: 0.5-1; the total concentration of the cross-linking agent and the inorganic oxide mixed solution is 0.1-0.9 wt%;
(4) and coating the membrane casting solution on a porous acetate fiber support, drying, spraying a cross-linking agent and inorganic oxide mixed solution, rolling by a hot-pressing composite roller, and drying to obtain the composite proton exchange membrane based on the porous acetate fiber support.
2. The method of claim 1, wherein: the mass ratio of the polymer proton conductor, the proton conduction enhancing additive, the inorganic oxide and the cross-linking agent is 1:0.1-0.15:0.05-0.15: 0.025-0.15.
3. The method of claim 1, wherein: in the step (2), the mass of the proton conduction enhancing additive is 5-15% of the mass of the polymer proton conductor.
4. The production method according to claim 1, characterized in that: in the step (3), the cross-linking agent is any one of dicumyl peroxide and benzoyl peroxide; the inorganic oxide is any one of nano zinc oxide and nano silicon dioxide.
5. The method of claim 1, wherein: in the step (4), the coating speed is 1-5m/min, and the coating thickness is 20-50 μm; the spraying flow rate is 5-10mL/min, and the spraying speed is 100-300 mm/s.
6. The method of claim 1, wherein: in the step (4), the drying temperature is 60-100 ℃ after coating; the rolling pressure is 1-15MPa, and the rolling temperature is 120-200 ℃; the drying temperature after spraying is 150-.
7. The production method according to any one of claims 1 to 6, characterized in that: the preparation method adopts continuous coating equipment, wherein a coating die head, a first oven, a spraying chamber, a pair of mutually meshed hot-pressing composite rollers, a second oven and a wind-up roller are sequentially arranged in the continuous coating equipment along the conveying direction of the composite proton exchange membrane; a spray head is arranged in the spray coating chamber; the continuous coating device also comprises a plurality of conveying rollers for conveying the composite proton exchange membrane forwards.
8. A composite proton exchange membrane based on a porous support of cellulose acetate, characterized in that it is prepared by the method of any one of claims 1 to 7.
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| CN101188301A (en) * | 2007-12-10 | 2008-05-28 | 华南理工大学 | A proton exchange film for direct carbinol fuel battery and its making method |
| CN101350418A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
| CN106046403A (en) * | 2016-05-31 | 2016-10-26 | 江苏师范大学 | Preparation method of composite proton exchange membrane based on hydrophilic porous supporting body |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101188301A (en) * | 2007-12-10 | 2008-05-28 | 华南理工大学 | A proton exchange film for direct carbinol fuel battery and its making method |
| CN101350418A (en) * | 2008-07-22 | 2009-01-21 | 山东东岳神舟新材料有限公司 | Microporous-film-and-fiber-reinforced multilayer fluorine-containing cross-linking doping ionic membrane and preparation method thereof |
| CN106046403A (en) * | 2016-05-31 | 2016-10-26 | 江苏师范大学 | Preparation method of composite proton exchange membrane based on hydrophilic porous supporting body |
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