CN117913331A - Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane - Google Patents
Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 160
- 150000003460 sulfonic acids Chemical class 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002715 modification method Methods 0.000 title claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 55
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- 238000005406 washing Methods 0.000 claims abstract description 38
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000620 organic polymer Polymers 0.000 claims abstract description 15
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract description 7
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 66
- 239000004693 Polybenzimidazole Substances 0.000 claims description 40
- 229920002480 polybenzimidazole Polymers 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002033 PVDF binder Substances 0.000 claims description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
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Abstract
The invention provides a proton exchange membrane modification method for an iron-chromium flow battery and a perfluorinated sulfonic acid composite membrane. The modification method comprises the following steps: soaking the perfluorinated sulfonic acid membrane in an acidic solution and/or an alkaline solution for washing, and then washing with deionized water to obtain a pretreated perfluorinated sulfonic acid membrane; immersing the pretreated perfluorinated sulfonic acid membrane in a solution of an organic polymer to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane, thereby obtaining a modified perfluorinated sulfonic acid membrane; and carrying out heat treatment on the modified perfluorinated sulfonic acid membrane to obtain the perfluorinated sulfonic acid composite membrane. The perfluorosulfonic acid composite membrane is prepared by the modification method. According to the invention, the perfluorinated sulfonic acid membrane is modified, and the organic polymer is used as the reinforcing phase, so that the novel perfluorinated sulfonic acid composite membrane is formed, and has high proton conductivity and good mechanical properties, and can improve the energy efficiency of the iron-chromium flow battery and reduce the capacity attenuation.
Description
Technical Field
The invention belongs to the technical field of energy storage, and particularly relates to a proton exchange membrane modification method for an iron-chromium flow battery and a perfluorinated sulfonic acid composite membrane.
Background
Excessive utilization of fossil energy brings problems to sustainable development of human beings, such as insufficient energy reserves, environmental pollution and the like. The new energy technology is widely concerned due to the advantages of cleanness, reproducibility and the like. The development of renewable energy sources can not only improve the energy source structure, but also solve the problems of global warming and the like. As large-scale energy storage equipment, the flow battery has the functions of peak clipping, valley filling and power grid stability maintenance. Flow batteries are one of the most promising large-scale energy storage technologies at present, and are receiving more and more attention because they can accelerate the utilization of renewable energy sources by solving the problems of discontinuous, unstable and uncontrollable. The iron-chromium flow battery has the advantages of low cost, high environmental adaptability and the like, is more and more concerned in the research, development and application of large-scale energy storage technology, and has better industrialization and market popularization and application prospects.
In a flow battery system, a perfluorosulfonic acid proton exchange membrane is an essential component, plays a key role in separating active reactant substances of two half batteries and preventing short circuit phenomenon in the operation process of a galvanic pile, and simultaneously plays a role in allowing transportation of charge carriers, and the two electrodes shuttle to form internal current to realize complete circuit. The proton exchange membrane needs to have high ion selectivity, can prevent cross contamination of electrolyte active substances, and meanwhile, the proton exchange membrane still needs to have high permeability and proton conductivity, so that quick passing of carriers is ensured, the internal resistance of the battery is reduced, and the proton exchange membrane also needs to have high chemical stability and high mechanical strength, so that the longer cycle life of the battery is ensured. Therefore, the improvement of the perfluorosulfonic acid proton exchange membrane to achieve the effects becomes one of the problems to be solved in the art.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a proton exchange membrane modification method for an iron-chromium flow battery. Aiming at the defects of the traditional perfluorosulfonic acid membrane, the invention aims to modify the perfluorosulfonic acid membrane, adopts organic matters as reinforcing phases to form a composite membrane, thereby improving the proton conductivity and the mechanical property of the perfluorosulfonic acid membrane and enabling the iron-chromium flow battery to realize better cycle performance.
Another object of the present invention is to provide a perfluorosulfonic acid composite membrane. The perfluorinated sulfonic acid composite membrane is prepared by the proton exchange membrane modification method for the iron-chromium flow battery.
In order to achieve the above object, a first aspect of the present invention provides a proton exchange membrane modification method for an iron-chromium flow battery, comprising the steps of:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in an acidic solution and/or an alkaline solution for washing, and then washing with deionized water to obtain a pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: immersing the pretreated perfluorinated sulfonic acid membrane in a solution of an organic polymer to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane, thereby obtaining a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and carrying out heat treatment on the modified perfluorinated sulfonic acid membrane to obtain a perfluorinated sulfonic acid composite membrane.
In the above method, preferably, in step (1), the acidic solution includes one or a combination of several of a hydrochloric acid solution, a hydrogen peroxide solution, a sulfuric acid solution, and the like, and the alkaline solution includes one or a combination of several of an ammonia water, a sodium hydroxide solution, a potassium hydroxide solution, and the like.
In the above method, preferably, in step (1), the concentration of the acidic solution and the basic solution is 0.1 to 5 mol/L, respectively.
In the above method, preferably, in step (1), the temperature of the washing is 20 to 100 ℃, more preferably 60 to 100 ℃; the total time of the washing is 0.5 to 8h hours, more preferably 1.5 to 8 h.
In the above method, preferably, in step (2), the organic polymer includes one or a combination of several of Polybenzimidazole (PBI), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyethyleneimine (PEI), and the like.
In the above method, preferably, in the step (2), the solution of the organic polymer is a solution formed by dissolving the organic polymer in an organic solvent including one or a combination of several of Dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), ethylene glycol dimethyl ether (GDME), and the like.
In the above method, preferably, in the step (2), the concentration of the organic polymer in the solution of the organic polymer is 0.5 to 10 g/L.
In the above method, preferably, in step (2), the soaking temperature is 20 to 60 ℃ and the time is 0.2 to 8h.
In the above method, preferably, in step (3), the heat treatment is performed at a temperature of 80 to 300 ℃ for a time of 4 to 12 h. The heat treatment process may be performed in an oven.
According to a preferred embodiment of the present invention, the proton exchange membrane modification method for an iron-chromium flow battery comprises the following steps:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5 mol/L for washing 0.5-2 h, then soaking in hydrochloric acid solution with the concentration of 1-5 mol/L for washing 0.5-2 h, and then soaking in deionized water for washing 0.5-2 h, wherein the washing temperature is 60-100 ℃, so as to obtain the pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: preparing 0.5-10 g/L of Polybenzimidazole (PBI) Dimethylformamide (DMF) solution, soaking the pretreated perfluorinated sulfonic acid membrane in the solution at room temperature for 0.2-8 h so as to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane and obtain a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and taking out the modified perfluorinated sulfonic acid membrane, and performing heat treatment on the membrane in an oven at 80-300 ℃ for 4-12 h to obtain the perfluorinated sulfonic acid composite membrane.
According to another preferred embodiment of the present invention, the proton exchange membrane modification method for an iron-chromium flow battery comprises the following steps:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5 mol/L for washing 0.5-2 h, then soaking in hydrochloric acid solution with the concentration of 1-5 mol/L for washing 0.5-2 h, and then soaking in deionized water for washing 0.5-2 h, wherein the washing temperature is 60-100 ℃, so as to obtain the pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: preparing 0.5-10 g/L of Polybenzimidazole (PBI) Dimethylformamide (DMF) solution as a first soaking solution; preparing 0.5-10 g/L of polyvinylidene fluoride (PVDF) Dimethylformamide (DMF) solution as a second soaking solution; soaking the pretreated perfluorinated sulfonic acid membrane in the first soaking liquid, adding the second soaking liquid, and soaking at room temperature for 0.2-8 h to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane to obtain a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: taking out the modified perfluorinated sulfonic acid membrane, and performing heat treatment on the membrane in an oven at 80-300 ℃ for 4-12 h to obtain a perfluorinated sulfonic acid composite membrane;
Wherein, more preferably, the mass ratio of Polybenzimidazole (PBI) to polyvinylidene fluoride (PVDF) is 1:3-3:1;
More preferably, the volume ratio of the first soaking liquid to the second soaking liquid is 1:1.
The invention also provides a perfluorinated sulfonic acid composite membrane prepared by the proton exchange membrane modification method for the iron-chromium flow battery.
The invention provides a proton exchange membrane modification method for an iron-chromium flow battery and a perfluorinated sulfonic acid composite membrane. Aiming at the defects of the existing perfluorosulfonic acid membrane, the perfluorosulfonic acid membrane is modified, and the organic polymer is used as the reinforcing phase, so that the novel perfluorosulfonic acid composite membrane is formed, and has high proton conductivity, high ion selectivity and good mechanical property, and can improve the energy efficiency of the iron-chromium flow battery and reduce the capacity attenuation.
The technical scheme of the invention has at least the following beneficial effects:
1. The perfluorinated sulfonic acid membrane modification technology provided by the invention has the advantages of simple and safe operation process and low cost, has low environmental requirements, and is suitable for large-scale application.
2. The perfluorinated sulfonic acid composite membrane prepared by the invention can improve the ion selectivity of the perfluorinated sulfonic acid membrane and ensure good mechanical performance while ensuring high proton conductivity, and further solves the problem of mutual strings of positive and negative electrolyte of the iron-chromium flow battery, thereby improving the stability of the battery, improving the energy efficiency of the battery, delaying the attenuation of the battery performance and enabling the iron-chromium flow battery to realize better cycle performance.
Drawings
Fig. 1 is an energy efficiency graph of the pretreated perfluorosulfonic acid membrane prepared in comparative example 1 applied to an iron-chromium flow battery.
Fig. 2 is an energy efficiency graph of the PBI/Nafion composite membrane prepared in comparative example 2 applied to an iron-chromium flow battery.
Fig. 3 is an energy efficiency graph of the Nafion/PBI composite membrane prepared in example 1 applied to an iron-chromium flow battery.
Fig. 4 is an energy efficiency graph of the Nafion/PBI/PVDF composite membrane prepared in example 2 applied to an iron-chromium flow battery.
Fig. 5 is a graph showing the discharge capacity decay rate of the pretreated perfluorosulfonic acid membrane prepared in comparative example 1 applied to an iron-chromium flow battery.
Fig. 6 is a graph showing the discharge capacity decay rate of the PBI/Nafion composite membrane prepared in comparative example 2 applied to an iron-chromium flow battery.
Fig. 7 is a graph showing the discharge capacity decay rate of the Nafion/PBI composite membrane prepared in example 1 applied to an iron-chromium flow battery.
FIG. 8 is a graph showing the discharge capacity decay rate of the Nafion/PBI/PVDF composite membrane prepared in example 2 applied to an iron-chromium flow battery.
FIG. 9 is a stress-strain curve of the pretreated perfluorosulfonic acid membrane prepared in comparative example 1.
FIG. 10 is a stress-strain curve of the PBI/Nafion composite membrane prepared in comparative example 2.
FIG. 11 is a stress-strain curve of the Nafion/PBI composite membrane prepared in example 1.
FIG. 12 is a stress-strain curve of the Nafion/PBI/PVDF composite membrane prepared in example 2.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Comparative example 1
The comparative example provides a pretreated perfluorosulfonic acid membrane, the preparation method of which comprises the following steps:
Proton exchange membrane pretreatment: cutting a perfluorinated sulfonic acid membrane (Nafion 212) with the size of 4.2cm multiplied by 8.2cm, soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5mol/L at 80 ℃ for washing 1 h, taking out, wiping cleanly, then soaking in hydrochloric acid solution with the concentration of 2.5 mol/L at 80 ℃ for washing 1 h, taking out, then soaking in deionized water at 80 ℃ for washing 0.5 h, and absorbing surface moisture by using absorbent paper to obtain the perfluorinated sulfonic acid membrane after pretreatment.
The energy efficiency of the battery at a current density of 140 mA cm -2 was analyzed by assembling an iron-chromium flow battery using the pretreated perfluorosulfonic acid membrane, the obtained energy efficiency graph is shown in fig. 1, and the discharge capacity decay rate graph is shown in fig. 5. The mechanical properties of the films were tested using a stretcher, and the stress-strain diagram is shown in fig. 9.
Comparative example 2
The comparative example provides a PBI/Nafion composite membrane, the preparation method comprises the following steps:
(1) Proton exchange membrane pretreatment: cutting a PBI film with the size of 4.2cm multiplied by 8.2cm, soaking the film in hydrogen peroxide solution with the concentration of 0.8-1.5mol/L at 80 ℃ for washing 1h, taking out and wiping the film clean, then soaking in hydrochloric acid solution with the concentration of 2.5 mol/L at 80 ℃ for washing 1h, taking out, then soaking in deionized water at 80 ℃ for washing 0.5 h, and sucking surface moisture by using absorbent paper to obtain a pretreated PBI film;
(2) Preparing a modified proton exchange membrane: completely dissolving 9.5 g perfluorinated sulfonic acid resin in 100 ml Dimethylformamide (DMF) solution to obtain perfluorinated sulfonic acid resin solution, soaking the pretreated PBI membrane in the perfluorinated sulfonic acid resin solution at room temperature for 3 h to form a reinforcing layer on the surface of the pretreated PBI membrane to obtain a modified proton exchange membrane;
(3) Forming a composite film: and taking out the modified proton exchange membrane, sucking the surface solution by using water absorption paper, and performing heat treatment on the surface solution in an oven at 180 ℃ for 8h to obtain the PBI/Nafion composite membrane.
The iron-chromium flow battery with the same structure as comparative example 1 was assembled using the PBI/Nafion composite membrane, and the battery energy efficiency at a current density of 140 mA cm -2 was analyzed, and the obtained energy efficiency graph was shown in fig. 2, and the discharge capacity decay rate graph was shown in fig. 6. The mechanical properties of the films were tested using a stretcher, and the stress-strain diagram is shown in fig. 10.
Example 1
The embodiment provides a Nafion/PBI composite membrane, and the preparation method comprises the following steps:
(1) Proton exchange membrane pretreatment: cutting a perfluorinated sulfonic acid membrane (Nafion 212) with the size of 4.2cm multiplied by 8.2cm, soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5mol/L at 80 ℃ for washing 1 h, taking out, wiping cleanly, then soaking in hydrochloric acid solution with the concentration of 2.5 mol/L at 80 ℃ for washing 1 h, taking out, then soaking in deionized water at 80 ℃ for washing 0.5 h, and absorbing surface moisture by using absorbent paper to obtain the perfluorinated sulfonic acid membrane after pretreatment;
(2) Preparing a modified proton exchange membrane: completely dissolving 0.5 g Polybenzimidazole (PBI) in 100 ml Dimethylformamide (DMF) solution to obtain a Dimethylformamide (DMF) solution of Polybenzimidazole (PBI), soaking the pretreated perfluorosulfonic acid membrane in the solution at room temperature for 3h to form a reinforcing layer on the surface of the pretreated perfluorosulfonic acid membrane to obtain a modified perfluorosulfonic acid membrane;
(3) Forming a composite film: and taking out the modified perfluorinated sulfonic acid membrane, sucking the surface solution by using absorbent paper, and performing heat treatment on the surface solution in an oven at 180 ℃ for 8h to obtain the Nafion/PBI composite membrane.
The iron-chromium flow battery with the same structure as comparative example 1 was assembled using the Nafion/PBI composite membrane, and the battery energy efficiency at a current density of 140 mA cm -2 was analyzed, and the obtained energy efficiency graph was shown in fig. 3, and the discharge capacity decay rate graph was shown in fig. 7. The mechanical properties of the films were tested using a stretcher, and the stress-strain diagram is shown in fig. 11.
Example 2
The embodiment provides a Nafion/PBI/PVDF composite membrane, and the preparation method comprises the following steps:
(1) Proton exchange membrane pretreatment: cutting a perfluorinated sulfonic acid membrane (Nafion 212) with the size of 4.2cm multiplied by 8.2cm, soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5mol/L at 80 ℃ for washing 1 h, taking out, wiping cleanly, then soaking in hydrochloric acid solution with the concentration of 2.5 mol/L at 80 ℃ for washing 1 h, taking out, then soaking in deionized water at 80 ℃ for washing 0.5 h, and absorbing surface moisture by using absorbent paper to obtain the perfluorinated sulfonic acid membrane after pretreatment;
(2) Preparing a modified proton exchange membrane: completely dissolving 0.3 g Polybenzimidazole (PBI) in 100 ml Dimethylformamide (DMF) solution to prepare a first soaking solution; completely dissolving 0.3 g polyvinylidene fluoride (PVDF) in 100 ml Dimethylformamide (DMF) solution to prepare a second soaking solution; soaking the pretreated perfluorinated sulfonic acid membrane in the first soaking liquid, adding the second soaking liquid, and soaking at room temperature for 3 h to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane to obtain a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and taking out the modified perfluorinated sulfonic acid membrane, sucking the surface solution by using absorbent paper, and performing heat treatment on the surface solution in an oven at 180 ℃ for 8h to obtain the Nafion/PBI/PVDF composite membrane.
The Nafion/PBI/PVDF composite membrane was used to assemble an iron-chromium flow battery having the same structure as comparative example 1, and the battery energy efficiency at a current density of 140 mA cm -2 was analyzed, and the obtained energy efficiency graph was shown in FIG. 4, and the discharge capacity decay rate graph was shown in FIG. 8. The mechanical properties of the films were tested using a stretcher, and the stress-strain diagram is shown in fig. 12.
As can be seen from the test results of comparative examples 1, 2, 1 and 2, the proton exchange membrane is modified by the method of the embodiment of the invention, so that the composite membrane has better mechanical property and chemical stability, ensures higher proton conductivity, avoids the problem of battery capacity attenuation caused by the mutual strings of positive and negative electrolyte, improves the stability and electrochemical performance of the battery, and enables the iron-chromium flow battery to realize better cycle performance.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (12)
1. A proton exchange membrane modification method for an iron-chromium flow battery, comprising the following steps:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in an acidic solution and/or an alkaline solution for washing, and then washing with deionized water to obtain a pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: immersing the pretreated perfluorinated sulfonic acid membrane in a solution of an organic polymer to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane, thereby obtaining a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and carrying out heat treatment on the modified perfluorinated sulfonic acid membrane to obtain a perfluorinated sulfonic acid composite membrane.
2. The method according to claim 1, wherein in step (1), the acidic solution comprises one or a combination of several of a hydrochloric acid solution, a hydrogen peroxide solution and a sulfuric acid solution, and the alkaline solution comprises one or a combination of several of an ammonia water, a sodium hydroxide solution and a potassium hydroxide solution;
In step (1), the concentration of the acidic solution and the alkaline solution is 0.1-5 mol/L, respectively.
3. The method of claim 1, wherein in step (1), the temperature of the washing is 20-100 ℃; the total time of the washing is 0.5-8 h hours.
4. The method of claim 1, wherein in step (2), the organic polymer comprises one or a combination of several of polybenzimidazole, polyvinylidene fluoride, polytetrafluoroethylene, and polyethyleneimine.
5. The method according to claim 1, wherein in the step (2), the solution of the organic polymer is a solution formed by dissolving the organic polymer in an organic solvent including one or a combination of several of dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and ethylene glycol dimethyl ether.
6. The method according to claim 1, wherein in step (2), the concentration of the organic polymer in the solution of the organic polymer is 0.5-10 g/L.
7. The method of claim 1, wherein in step (2), the soaking is performed at a temperature of 20-60 ℃ for a time of 0.2-8 h.
8. The method according to claim 1, wherein in step (3), the heat treatment is performed at a temperature of 80-300 ℃ for a time of 4-12 h.
9. The method of claim 1, wherein the proton exchange membrane modification method for an iron-chromium flow battery comprises the steps of:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5 mol/L for washing 0.5-2 h, then soaking in hydrochloric acid solution with the concentration of 1-5 mol/L for washing 0.5-2 h, and then soaking in deionized water for washing 0.5-2 h, wherein the washing temperature is 60-100 ℃, so as to obtain the pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: preparing 0.5-10 g/L of polybenzimidazole dimethylformamide solution, soaking the pretreated perfluorinated sulfonic acid membrane in the solution at room temperature for 0.2-8 h so as to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane and obtain a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and taking out the modified perfluorinated sulfonic acid membrane, and performing heat treatment on the membrane in an oven at 80-300 ℃ for 4-12 h to obtain the perfluorinated sulfonic acid composite membrane.
10. The method of claim 1, wherein the proton exchange membrane modification method for an iron-chromium flow battery comprises the steps of:
(1) Proton exchange membrane pretreatment: soaking the perfluorinated sulfonic acid membrane in hydrogen peroxide solution with the concentration of 0.8-1.5 mol/L for washing 0.5-2 h, then soaking in hydrochloric acid solution with the concentration of 1-5 mol/L for washing 0.5-2 h, and then soaking in deionized water for washing 0.5-2 h, wherein the washing temperature is 60-100 ℃, so as to obtain the pretreated perfluorinated sulfonic acid membrane;
(2) Preparing a modified proton exchange membrane: preparing 0.5-10 g/L of polybenzimidazole dimethylformamide solution as a first soaking solution; preparing 0.5-10 g/L of dimethylformamide solution of polyvinylidene fluoride as a second soaking solution; soaking the pretreated perfluorinated sulfonic acid membrane in the first soaking liquid, adding the second soaking liquid, and soaking at room temperature for 0.2-8 h to form a reinforcing layer on the surface of the pretreated perfluorinated sulfonic acid membrane to obtain a modified perfluorinated sulfonic acid membrane;
(3) Forming a composite film: and taking out the modified perfluorinated sulfonic acid membrane, and performing heat treatment on the membrane in an oven at 80-300 ℃ for 4-12 h to obtain the perfluorinated sulfonic acid composite membrane.
11. The method of claim 10, wherein the mass ratio of polybenzimidazole to polyvinylidene fluoride is 1:3-3:1; the volume ratio of the first soaking liquid to the second soaking liquid is 1:1.
12. A perfluorosulfonic acid composite membrane prepared by the proton exchange membrane modification method for an iron-chromium flow battery according to any one of claims 1 to 11.
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