CN117700792A - Composite proton exchange membrane for vanadium redox flow battery and preparation method thereof - Google Patents
Composite proton exchange membrane for vanadium redox flow battery and preparation method thereof Download PDFInfo
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- CN117700792A CN117700792A CN202311672996.6A CN202311672996A CN117700792A CN 117700792 A CN117700792 A CN 117700792A CN 202311672996 A CN202311672996 A CN 202311672996A CN 117700792 A CN117700792 A CN 117700792A
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- 239000012528 membrane Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 35
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 238000005266 casting Methods 0.000 claims description 20
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical compound NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001456 vanadium ion Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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Classifications
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a composite proton exchange membrane for a vanadium redox flow battery and a preparation method thereof, belonging to the fields of polymer chemistry and vanadium redox flow batteries. The invention firstly prepares the sulfonated polybenzimidazole and the modified metal organic framework structure, and then blends the sulfonated polybenzimidazole and the modified metal organic framework structure. The proton exchange membrane is prepared according to the weight percentage and comprises the following components: 96-99% sulfonated polybenzimidazole and 1-4% modified metal organic frameA frame structure. The proton conductivity of the composite proton exchange membrane is as high as 30.8mS cm ‑1 And at 60mA cm ‑2 The energy efficiency was 83.81% at the current density of (c), showing good battery performance.
Description
The authors: wang Shuang, high-pass
Technical Field
The invention belongs to the fields of polymer chemistry and vanadium redox flow batteries, and relates to a composite proton exchange membrane for a vanadium redox flow battery and a preparation method thereof.
Background
Vanadium redox flow batteries are a large energy storage system that achieves the interconversion of electrical and chemical energy by the change in valence state of vanadium ions. The device has the advantages of high charge-discharge response speed, environmental friendliness, low cost, flexible design, long service life and the like, and is widely paid attention to. The proton exchange membrane is used as a core component of the proton exchange membrane to determine the performance and efficiency of the battery. Currently, commercial Nafion-series membranes are commonly used membranes in flow batteries, which have high proton conductivity, excellent mechanical properties, and good chemical stability. However, the expensive cost and serious vanadium ion crossover problems limit their use and further development in flow batteries. Therefore, research and development of a new generation of proton exchange membranes has become a current research hotspot.
Disclosure of Invention
The invention aims to provide a composite proton exchange membrane for a vanadium redox flow battery and a preparation method thereof, wherein the composite proton exchange membrane has high proton conductivity and very good battery efficiency, and is used for preparing the composite proton exchange membrane at 60mA cm -2 At a current density of 83.81% of its energy efficiency. Meanwhile, the preparation method is simple in process and low in cost.
The invention firstly provides a composite proton exchange membrane for a vanadium redox flow battery, which comprises the following components in percentage by weight:
sulfonated polybenzimidazole: 96 to 99 percent
Modified metal organic framework structure: 1 to 4 percent of
The invention also provides a preparation method of the composite proton exchange membrane for the vanadium redox flow battery, which comprises the following steps:
step one: synthesizing sulfonated polybenzimidazole;
step two: respectively dissolving sulfonated polybenzimidazole and a modified metal organic framework in an organic solvent, and then mixing the solutions to obtain a casting solution;
step three: and (3) casting the casting solution obtained in the step two into a film by adopting a casting method, thus obtaining the composite proton exchange film for the vanadium redox flow battery.
Preferably, the preparation method of the sulfonated polybenzimidazole comprises the following steps: adding polyphosphoric acid and biphenyltetramine into a reaction container, adding isophthalic acid and 5-sulfonic group isophthalic acid after the biphenyltetramine is dissolved, and stirring and reacting for 6 hours at 200 ℃ to obtain sulfonated polybenzimidazole.
Preferably, the molar ratio of isophthalic acid to 5-sulfoisophthalic acid is 1:1.
preferably, the preparation method of the modified metal organic framework structure comprises the following steps: and adding trimesic acid and zirconium oxychloride octahydrate into the mixed solution of N, N-dimethylformamide/formic acid, and pouring the mixed solution into a reaction kettle to react for 2 days at 130 ℃ to obtain the MOF-808. Then MOF-808 and ethylenediamine tetraacetic acid disodium salt are dissolved in deionized water and reacted for 1 day at 60 ℃ to obtain a modified metal organic framework structure: MOF-808-EDTA (MGE).
Preferably, the molar ratio of the trimesic acid to the zirconium oxychloride octahydrate is 1:3, a step of; the volume ratio of N, N-dimethylformamide to formic acid is 1:1.
Preferably, the organic solvent is dimethyl sulfoxide.
The beneficial effects of the invention are that
The invention firstly provides a composite proton exchange membrane for a vanadium redox flow battery, which is characterized by comprising 96-99% of sulfonated polybenzimidazole and 1-4% of modified metal organic framework structure according to weight percentage. The permeability of vanadium ions can be reduced in the proton exchange membrane due to the compact structure of the matrix polybenzimidazole; the sulfonic acid groups act as proton carriers and proton donors to facilitate the construction of hydrogen bond network structures, which helps to increase proton conductivity and reduce area resistance. The modified metal-organic framework structure has amino and carboxyl groups, which provide additional proton transport channels, and the acid-base pair effect between the amino and sulfonic acid groups can enhance the interaction forces of the matrix and the modified metal-organic framework structure. Meanwhile, the modified metal organic framework structure has proper aperture, and can effectively prevent vanadium ions from permeating, thereby realizing higher ion selectivity. The experimental results show that: the proton conductivity of the composite proton exchange membrane is as high as 30.8mS cm -1 And at 60mAcm -2 The energy efficiency was 83.81% at the current density of (c), showing good battery performance.
The invention also provides a preparation method of the composite proton exchange membrane for the vanadium redox flow battery, which is to prepare the sulfonated polybenzimidazole by a solution polymerization method and prepare the composite proton exchange membrane by a blending method.
Detailed description of the preferred embodiments
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to further illustrate the features and advantages of the invention and are not limiting of the patent claims of the invention. The invention firstly provides a composite proton exchange membrane for a vanadium redox flow battery, which comprises the following materials in percentage by mass:
sulfonated polybenzimidazole: 96 to 99 percent
Modified metal organic framework structure: 1 to 4 percent of
The invention also provides a preparation method of the composite proton exchange membrane for the vanadium redox flow battery, which comprises the following steps:
step one: synthesizing sulfonated polybenzimidazole;
step two: respectively dissolving sulfonated polybenzimidazole and a modified metal organic framework in an organic solvent, and then mixing the solutions to obtain a casting solution;
step three: and (3) casting the casting solution obtained in the step two into a film by adopting a casting method, thus obtaining the composite proton exchange film for the vanadium redox flow battery.
Preferably, the preparation method of the sulfonated polybenzimidazole comprises the following steps: adding polyphosphoric acid and biphenyltetramine into a reaction container, adding isophthalic acid and 5-sulfonic group isophthalic acid after the biphenyltetramine is dissolved, and stirring and reacting for 6 hours at 200 ℃ to obtain sulfonated polybenzimidazole. Wherein the molar ratio of the isophthalic acid to the 5-sulfoisophthalic acid is 1:1. the preparation method of the modified metal organic framework structure comprises the following steps: and adding trimesic acid and zirconium oxychloride octahydrate into the mixed solution of N, N-dimethylformamide/formic acid, and pouring the mixed solution into a reaction kettle to react for 2 days at 130 ℃ to obtain the MOF-808. Then MOF-808 and ethylenediamine tetraacetic acid disodium salt are dissolved in deionized water and reacted for 1 day at 60 ℃ to obtain a modified metal organic framework structure: MOF-808-EDTA (MGE). Wherein the molar ratio of the trimesic acid to the zirconium oxychloride octahydrate is 1:3, a step of; the volume ratio of N, N-dimethylformamide to formic acid is 1:1.
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the sulfonated polybenzimidazole comprises the following steps: under the protection of nitrogen, placing polyphosphoric acid into a four-mouth bottle, stirring and heating for 1h, adding 1mol of biphenyltetramine when the polyphosphoric acid is in a transparent liquid state, controlling the temperature at 140 ℃, adding isophthalic acid and 5-sulfoisophthalic acid when the biphenyltetramine is completely dissolved, stirring and heating for 1h, starting heating, controlling the temperature at 200 ℃ for reacting for 6h, discharging the obtained brown viscous liquid into excessive water, and displaying a strip shape. 150g NaHCO was added thereto 3 And (3) neutralizing, checking with pH test paper until the solution is neutral, washing with deionized water for several times, and drying in an oven to obtain the sulfonated polybenzimidazole.
Example 2
The preparation method of the sulfonated polybenzimidazole comprises the following steps: under the protection of nitrogen, placing polyphosphoric acid into a four-mouth bottle, stirring and heating for 2 hours, adding 1mol of biphenyltetramine when the polyphosphoric acid is in a transparent liquid state, controlling the temperature at 130 ℃, adding isophthalic acid and 5-sulfoisophthalic acid when the biphenyltetramine is completely dissolved, stirring and heating for 1 hour, starting heating, controlling the temperature at 220 ℃ for reacting for 5 hours, discharging the obtained brown viscous liquid into excessive water, and displaying a strip shape. 130g NaHCO was added thereto 3 And (3) neutralizing, checking with pH test paper until the solution is neutral, washing with deionized water for several times, and drying in an oven to obtain the sulfonated polybenzimidazole.
Example 3
The preparation method of the sulfonated polybenzimidazole comprises the following steps: placing polyphosphoric acid into a four-mouth bottle under the protection of nitrogen, stirring and heating for 3h, adding 1mol of biphenyltetramine when the polyphosphoric acid is in a transparent liquid state, controlling the temperature at 120 ℃, and completely dissolving the biphenyltetramine when the polyphosphoric acid is in a transparent liquid stateAdding isophthalic acid and 5-sulfoisophthalic acid, stirring and heating for 1h, starting to raise the temperature, controlling the temperature to be 230 ℃ for reaction for 4h, discharging the obtained brown viscous liquid into excessive water, and taking the product into a strip shape. 160g NaHCO was added thereto 3 And (3) neutralizing, checking with pH test paper until the solution is neutral, washing with deionized water for several times, and drying in an oven to obtain the sulfonated polybenzimidazole.
Example 4
1mol of trimesic acid and 3mol of zirconium oxychloride octahydrate were added to the mixed solution of N, N-dimethylformamide/formic acid to be sufficiently dissolved, and poured into a reaction kettle to be heated at 130 ℃ for reaction for 2 days, and then the obtained white powder was washed with N, N-dimethylformamide several times to remove unreacted substances. Finally, the resulting MOF-808 was kept in a vacuum oven at 60 ℃ to remove excess N, N-dimethylformamide. Subsequently, MOF-808 and disodium ethylenediamine tetraacetate were added to deionized water and reacted at 60℃for 1 day to obtain a modified metal organic framework structure: MOF-808-EDTA (MGE).
Example 5
1mol of trimesic acid and 3mol of zirconium oxychloride octahydrate were added to the mixed solution of N, N-dimethylformamide/formic acid to be sufficiently dissolved, and poured into a reaction kettle to be heated at 135 ℃ for reaction for 2 days, and then the obtained white powder was washed with N, N-dimethylformamide several times to remove unreacted substances. Finally, the resulting MOF-808 was kept in a vacuum oven at 60 ℃ to remove excess N, N-dimethylformamide. Subsequently, MOF-808 and disodium ethylenediamine tetraacetate were added to deionized water and reacted at 45℃for 2 days to give a modified metal organic framework structure: MOF-808-EDTA (MGE).
Example 6
The sulfonated polybenzimidazole obtained in example 1 was dissolved in dimethyl sulfoxide to obtain a homogeneous solution, and then, an equimolar amount of the modified metal organic framework structure obtained in example 4 was added thereto, followed by stirring for 1 hour to obtain a homogeneous casting solution. The solution was filtered through a filter cloth onto a glass plate, placed in a vacuum oven at 60 ℃ for 4 hours, and the resulting film was dried at 90 ℃. Finally, the composite proton exchange membrane is obtained. Wherein the casting solution comprises the following components in percentage by weight:
sulfonated polybenzimidazole: 96 percent of
Modified metal organic framework structure: 4%
Example 7
The sulfonated polybenzimidazole obtained in example 1 was dissolved in dimethyl sulfoxide to obtain a homogeneous solution, and then, an equimolar amount of the modified metal organic framework structure obtained in example 4 was added thereto, followed by stirring for 1 hour to obtain a homogeneous casting solution. The solution was filtered through a filter cloth onto a glass plate, placed in a vacuum oven at 60 ℃ for 4 hours, and the resulting film was dried at 90 ℃. Finally, the composite proton exchange membrane is obtained. Wherein the casting solution comprises the following components in percentage by weight:
sulfonated polybenzimidazole: 97%
Modified metal organic framework structure: 3%
Example 8
The sulfonated polybenzimidazole obtained in example 1 was dissolved in dimethyl sulfoxide to obtain a homogeneous solution, and then, an equimolar amount of the modified metal organic framework structure obtained in example 4 was added thereto, followed by stirring for 1 hour to obtain a homogeneous casting solution. The solution was filtered through a filter cloth onto a glass plate, placed in a vacuum oven at 60 ℃ for 4 hours, and the resulting film was dried at 90 ℃. Finally, the composite proton exchange membrane is obtained. Wherein the casting solution comprises the following components in percentage by weight:
sulfonated polybenzimidazole: 98 percent of
Modified metal organic framework structure: 2%
Example 9
The sulfonated polybenzimidazole obtained in example 1 was dissolved in dimethyl sulfoxide to obtain a homogeneous solution, and then, an equimolar amount of the modified metal organic framework structure obtained in example 4 was added thereto, followed by stirring for 1 hour to obtain a homogeneous casting solution. The solution was filtered through a filter cloth onto a glass plate, placed in a vacuum oven at 60 ℃ for 4 hours, and the resulting film was dried at 90 ℃. Finally, the composite proton exchange membrane is obtained. Wherein the casting solution comprises the following components in percentage by weight:
sulfonated polybenzimidazole: 99 percent of
Modified metal organic framework structure: 1%
Example 10
The proton exchange membranes obtained in example 6, example 7, example 8 and example 9 were subjected to performance characterization and testing. The proton exchange membrane obtained in example 8 had a proton conductivity as high as 30.8mS cm -1 And at 60mAcm -2 The energy efficiency was 83.81%, and excellent battery performance was exhibited.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core concept, and it should be pointed out that it is possible for a person skilled in the art to make several improvements and modifications without departing from the principle of the invention, which also falls within the scope of protection of the claims of the present invention.
Claims (7)
1. The composite proton exchange membrane for the vanadium redox flow battery is characterized by comprising the following components in percentage by weight:
sulfonated polybenzimidazole: 96 to 99 percent
Modified metal organic framework structure: 1 to 4 percent.
2. The method for preparing a composite proton exchange membrane for a vanadium redox flow battery according to claim 1, comprising the following steps:
step one: synthesizing sulfonated polybenzimidazole;
step two: respectively dissolving sulfonated polybenzimidazole and a modified metal organic framework in an organic solvent, and then mixing the solutions to obtain a casting solution;
step three: and (3) casting the casting solution obtained in the step two into a film by adopting a casting method, thus obtaining the composite proton exchange film for the vanadium redox flow battery.
3. The method for preparing the composite proton exchange membrane for the vanadium redox flow battery according to claim 2, wherein the method for preparing the sulfonated polybenzimidazole is as follows: adding polyphosphoric acid and biphenyltetramine into a reaction container, adding isophthalic acid and 5-sulfonic group isophthalic acid after the biphenyltetramine is dissolved, and stirring and reacting for 6 hours at 200 ℃ to obtain sulfonated polybenzimidazole.
4. The method for preparing a composite proton exchange membrane for vanadium redox flow battery according to claim 3, wherein the molar ratio of isophthalic acid to 5-sulfonic isophthalic acid is 1:1.
5. the method for preparing a composite proton exchange membrane for a vanadium redox flow battery according to claim 2, wherein the method for preparing the modified metal-organic framework structure is as follows: and adding trimesic acid and zirconium oxychloride octahydrate into the mixed solution of N, N-dimethylformamide/formic acid, and pouring the mixed solution into a reaction kettle to react for 2 days at 130 ℃ to obtain the MOF-808. Then MOF-808 and ethylenediamine tetraacetic acid disodium salt are dissolved in deionized water and reacted for 1 day at 60 ℃ to obtain a modified metal organic framework structure: MOF-808-EDTA (MGE).
6. The method for preparing a composite proton exchange membrane for vanadium redox flow battery according to claim 5, wherein the molar ratio of trimesic acid to zirconium oxychloride octahydrate is 1:3, a step of; the volume ratio of N, N-dimethylformamide to formic acid is 1:1.
7. The method for preparing a composite proton exchange membrane for a vanadium redox flow battery according to claim 2, wherein the organic solvent is dimethyl sulfoxide.
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