CN113036174B - Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof - Google Patents

Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof Download PDF

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CN113036174B
CN113036174B CN201911250050.4A CN201911250050A CN113036174B CN 113036174 B CN113036174 B CN 113036174B CN 201911250050 A CN201911250050 A CN 201911250050A CN 113036174 B CN113036174 B CN 113036174B
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membrane
porous ion
copolymer
polymer resin
solvent
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CN113036174A (en
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袁治章
李先锋
胡静
刘晓奇
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • 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
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses an application of an organic skeleton copolymer supported porous ion conduction membrane in a flow battery. The film is prepared by dissolving a soluble organic skeleton copolymer precursor A in a casting solution, coating the casting solution on a support body and carrying out phase inversion in a non-solvent containing an organic skeleton copolymer precursor B, wherein the precursor A and the precursor B generate the organic skeleton copolymer in situ in the film during the film forming process. And (3) treating, drying and acid-washing the prepared porous ion-conducting membrane containing the organic framework copolymer to prepare the porous ion-conducting membrane supported by the organic framework copolymer. The designed and prepared porous ion conduction membrane has good battery performance in a flow battery, particularly in an all-vanadium flow battery.

Description

Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof
Technical Field
The invention relates to preparation of an organic framework copolymer supported porous ion-conducting membrane, in particular to application of the membrane in a flow battery.
Background
The flow battery energy storage technology has the advantages of environmental friendliness, high safety, independent design of power and capacity, high life cycle cost performance and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, peak clipping and valley filling of emergency power supply systems, standby power stations and power systems and the like. As a key material of the flow battery, the ion conduction membrane plays a role in blocking the mutual series of positive and negative active substances and transferring charge balancing ions to form a battery internal loop, and the physical and chemical properties and the cost directly determine the performance and the cost of a battery system. The perfluorinated sulfonic acid ion exchange membrane is the most commonly used ion exchange membrane of the current flow battery, and the membrane material has the advantages of high proton conductivity and good chemical stability; however, such membrane materials are very expensive, and the large-scale application of the flow battery is limited due to the fact that the battery self-discharge and the capacity attenuation are serious because of poor ion selectivity in the all-vanadium flow battery system. The non-fluorine ion exchange membrane has the advantages of high ion selectivity, low cost and the like, but the oxidation stability of the membrane material is poor due to the introduction of an ion exchange group, so that the requirement of the all-vanadium redox flow battery on long-term operation cannot be met; the non-fluorine porous ion conduction membrane realizes the separation of active substances and the separation of charge balance ions through the pore size sieving effect, and effectively solves the problems of high price of the perfluorinated sulfonic acid ion exchange membrane and poor oxidation stability of the non-fluorine ion exchange membrane. Then, there are generally two cases of porous ion-conducting membranes prepared by conventional phase inversion methods: (1) the pore structure of the membrane is small enough that such membranes have high ion selectivity, but ion conductivity is generally poor; (2) the pore structure of the membrane is large enough that such membranes have high ionic conductivity, but ion selectivity is generally poor. Porous ion-conducting membranes prepared by this method generally cannot achieve both high ion selectivity and high ion selectivity, i.e., the ion selectivity of the membrane and the trade-off effect between the ion-conducting membranes.
Patent CN109659589A discloses a screening method of a polymer porous ion-conducting membrane for a flow battery in a solvent treatment process, which utilizes the strength of polymer-solvent interaction and the volatility of a solvent to realize controllable preparation of the structure and performance of the porous ion-conducting membrane. However, the method needs to make the pore diameter of the porous ion-conducting membrane before solvent treatment large enough (i.e. enough hydrophilicity regulator needs to be added into the membrane casting solution before membrane casting to obtain a large enough pore structure in the membrane forming process, and the coulombic efficiency of the all-vanadium redox flow battery assembled by the porous ion-conducting membrane before solvent treatment is low enough), so that the method has certain limitations.
Disclosure of Invention
In order to solve the problems, the invention prepares the organic framework copolymer supported porous ion-conducting membrane, and the porous ion-conducting membrane with low pore diameter (namely the all-vanadium redox flow battery single cell assembled by the porous ion-conducting membrane before being treated by a solvent has higher coulombic efficiency) is ensured not to collapse in the treatment process by utilizing the supporting effect of the organic framework copolymer on the membrane pores in the treatment process of the porous ion-conducting membrane, so that the controllable design between the structure and the performance of the porous ion-conducting membrane is realized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an organic skeleton copolymer supported porous ion-conducting membrane is prepared by the following steps:
(1) dissolving a high molecular resin and a soluble organic skeleton copolymer precursor A in an organic solvent to form a homogeneous solution, and then uniformly coating the homogeneous solution on a substrate;
(2) putting the matrix containing the casting solution into a non-solvent containing an organic framework copolymer precursor B, and performing phase inversion to obtain a porous ion-conducting membrane supported by the organic framework copolymer;
(3) the porous ion-conducting membrane supported by the organic framework copolymer is treated and dried for a certain time, and the organic framework copolymer in the porous ion-conducting membrane can effectively prevent the collapse problem of the inner pore structure of the membrane in the drying process;
(4) and (4) placing the membrane subjected to drying treatment in the step (3) in an acid solution to remove the organic framework copolymer in the membrane pores, so as to obtain the porous ion-conducting membrane with a complete pore structure.
The preparation method of the organic skeleton copolymer supported porous ion-conducting membrane comprises the following steps of (1) preparing a porous ion-conducting membrane by using a polymer resin, wherein the polymer resin comprises two types of polymer resins:
the first type is composed of one or more than two of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyether ketone, polytetrafluoroethylene, polyvinylidene fluoride, polybenzimidazole, polyolefin and chloromethylated polysulfone;
the second type is formed by mixing one or more than two types of first type polymer resin with one or more than two types of water-soluble polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and polyquaternary ammonium salt, wherein the mass ratio of the first type polymer resin to the water-soluble polymer resin is 100% (namely, the first type polymer resin can be completely composed) and 40%, preferably 95% -65%;
in the preparation method of the porous ion-conducting membrane supported by the organic framework copolymer, the precursor A of the organic framework copolymer in the step (1) is as follows: one or more of imidazole, methyl imidazole, 4, 5-dicarboxylimidazole, 4-hydroxymethyl imidazole hydrochloride, imidazole-4-ethyl formate, imidazole-4-methyl formate and 1H-imidazole-4-carboxylic acid;
in the preparation method of the organic framework copolymer supported porous ion-conducting membrane, the organic solvent in the step (1) is one or more than two of dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF);
in the preparation method of the porous ion-conducting membrane supported by the organic skeleton copolymer, the precursor B of the organic skeleton copolymer in the step (2) is as follows: one or more of zinc chloride, zinc bromide, zinc acetate, zinc sulfate and zinc nitrate;
in the preparation method of the organic skeleton copolymer supported porous ion conduction membrane, the non-solvent in the step (2) is water or alcohol CnH2n+2O (n is a positive integer of 1-6), and ketone CnH2nO (n is a positive integer of 3 to 8) and alkanes CnH2n+2(n is a positive integer of 5 to 10);
in the preparation method of the porous ion-conducting membrane supported by the organic framework copolymer, the treatment method of the membrane in the step (3) comprises the following steps: soaking the ion-conducting membrane prepared in the step (2) in a non-solvent for at least 10 minutes, and drying at room temperature-80 ℃ for at least 5 minutes; wherein the temperature is preferably room temperature to 60 ℃; the drying time is preferably 30 to 120 minutes;
in the preparation method of the organic skeleton copolymer supported porous ion-conducting membrane, the acidic solution in the step (4) is: one or more than two of acetic acid solution, hydrochloric acid solution, sulfuric acid solution, methanesulfonic acid solution, phosphoric acid solution and nitric acid solution; wherein the acid concentration is 1-30 wt%, preferably 5-20 wt%.
The invention has the following beneficial results:
1. the porous ion-conducting membrane supported by the organic skeleton copolymer prepared by the invention can effectively prevent the collapse problem of the membrane pore structure in the drying process of the porous ion-conducting membrane after solvent treatment, and realize the controllable design between the structure and the performance of the porous ion-conducting membrane.
2. In the preparation step 2), the organic skeleton copolymer is generated in situ in the film by using the organic skeleton copolymer precursor A and the organic skeleton precursor B in the film casting solution, and can be uniformly distributed in the film, so that the problem of nonuniform distribution of the organic skeleton copolymer in the film caused by directly blending the film casting solution and the organic skeleton copolymer is solved.
3. The organic skeleton copolymer generated in situ in the film forming process of the porous ion-conducting membrane supported by the organic skeleton copolymer can be completely removed by a dilute acid solution, so that the integrity of the pore structure of the diaphragm is kept, and the problem of the reduction of the ionic conductivity of the film caused by the traditional organic and inorganic particle pore-filling support is solved, thereby ensuring the ionic conductivity of the prepared membrane and endowing the battery with high coulombic efficiency and voltage efficiency.
4. The porous ion-conducting membrane supported by the organic skeleton copolymer widens the preparation method of membrane materials for the flow battery.
Drawings
FIG. 1 is a sectional topography (a) and a sectional topography enlarged view (b) of a PES/PVP porous ion-conducting membrane in comparative example 1 after drying treatment.
FIG. 2 all-vanadium redox flow battery single cell assembled by different membranes at 80mA cm-2Wherein M1 represents PES- (PVP + ZIF) porous ion-conducting membrane, and the membrane is treated by 10 wt% dilute hydrochloric acid solution after being treated by solvent and dried; m2 represents PES- (PVP + ZIF) porous ion-conducting membrane, which is not treated with solvent, dried, and treated with 10 wt% dilute hydrochloric acid solution; m3 represents PES-PVP porous ion conduction membrane, without solvent treatment and drying process; m4 represents PES-PVP porous ion conductive membrane, which is treated by solvent and dried.
FIG. 3 is a topographical view of an organic backbone copolymer supported porous ion conducting membrane. (a) A cross-sectional topography of the porous ion-conducting membrane supported by the organic framework copolymer (without solvent treatment and drying process); (b) a cross-sectional profile of the organic-framework copolymer-supported porous ion-conducting membrane after treatment with a 10 wt% dilute hydrochloric acid solution; (c) FIG. (a) an enlarged view of a part of the cortex; (d) FIG. (b) is a magnified view of a part of the skin layer.
FIG. 4 shows that the unit cell of the all-vanadium redox flow battery assembled by the M1 membrane and the Nafion 115 membrane is 40-200mA cm-2Cell performance under operating current density conditions.
Detailed Description
The performance test conditions of the all-vanadium redox flow battery are as follows: the positive electrode and the negative electrode both adopt carbon felts as electrodes, and the electrolyte of the positive electrode is 1.5mol/LVO2+/VO2 ++3mol/L H2SO4A solution; the electrolyte of the negative electrode is 1.5mol/LV2+/V3++3mol/L H2SO4A solution; the volumes of the positive electrolyte and the negative electrolyte are respectively 60 mL; the battery adopts a constant current charging and discharging mode and is charged at 80mA cm-2Under the current density condition of (1) to a cut-off voltage of 1.55V, and then under the voltage cut-off condition of 80mA cm-2Is discharged to 1.0V under the current density condition of (1).
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
PES/(PVP + imidazole) is taken as a base material, and the PES/(PVP + imidazole) is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 30%, wherein the mass ratio of the PES to the PVP is 9: 1, the mass ratio of PVP to imidazole is 1: 1; pouring the blended solution on a clean and flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, then immersing the whole body in an aqueous solution containing zinc chloride with the mass fraction of 3 wt% for 700s, in the film forming process, generating ZIF in situ in the film by imidazole in the casting solution and zinc chloride in a non-solvent, and preparing a PES- (PVP + ZIF) porous ion conduction film (expressed by M2) with the thickness of 75 μ M at 25 ℃. From FIG. 3a, it can be seen that the prepared membrane has a significant finger-shaped pore structure in cross section, and further the cross-sectional skin structure is enlarged (FIG. 3c), it can be seen that there is a significant lamellar structure in the cross-sectional skin structureZIF (thickness: 80nm) in the presence of a catalyst. Soaking the membrane in 10 wt% dilute hydrochloric acid solution to remove ZIF generated in the membrane to obtain a ZIF-free PES-PVP porous ion-conducting membrane with a membrane layer containing micro-nano pore structure, and applying the membrane layer in an all-vanadium flow battery at 80mA cm-2Under the operating current density condition of (2), the coulombic efficiency of the battery is 80.45%, the voltage efficiency is 89.51%, and the energy efficiency is 72.01%.
Example 2
PES/(PVP + imidazole) is taken as a base material, and the PES/(PVP + imidazole) is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 30%, wherein the mass ratio of the PES to the PVP is 9: 1, the mass ratio of PVP to imidazole is 1: 1; pouring the blending solution on a clean and flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, then immersing the whole body in zinc chloride solution containing 3 wt% of mass fraction for 700s, in the film forming process, in-situ generating ZIF in imidazole in the film casting solution and zinc chloride in a non-solvent in the film, and preparing the PES- (PVP + ZIF) porous ion conduction film with the thickness of 75 μm at 25 ℃. Soaking the PES- (PVP + ZIF) porous ion-conducting membrane prepared by the method in ethanol for 30 minutes, and then drying at room temperature for 60 minutes, wherein in the drying process, the ZIF in the membrane pores can maintain the pore structure of the membrane pores unchanged, so that the collapse of the membrane pore structure is prevented. And soaking the dried PES- (PVP + ZIF) porous ion-conducting membrane in 10 wt% of dilute hydrochloric acid solution to remove ZIF generated in the membrane, thereby obtaining a PES-PVP porous ion-conducting membrane (expressed by M1) without ZIF. From FIG. 3b, it can be seen that the cross section of the prepared membrane is in a significant finger-shaped pore structure, and the cross-sectional cortical structure is further enlarged (FIG. 3d), and it can be seen that after treatment with 10 wt% dilute hydrochloric acid solution, ZIF is substantially removed by hydrochloric acid, and at the same time, the cross-sectional pore structure is well maintained, which facilitates the conduction of charge balancing ions and has a good barrier effect on active substances. The material is used in an all-vanadium flow battery with the density of 80mAcm-2The coulombic efficiency of the cell was 96.70%, the voltage efficiency was 89.11%, and the energy efficiency was 86.17% (fig. 2).
The electrochemical performance of the M1 membrane was further tested and assembled with a Nafion 115 membraneThe performance of the all-vanadium redox flow battery is compared, and the result is shown in fig. 4. It can be seen that the current density is 40-200mA cm-2Under the condition of working current density, the all-vanadium redox flow battery assembled by the M1 film has higher coulombic efficiency and energy efficiency, so that the all-vanadium redox flow battery has a better application prospect in practical application.
Example 3
PES/imidazole is taken as a base material, and the PES/imidazole is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 26%, wherein the mass ratio of PES to imidazole is 8: 2, pouring the blending solution on a clean and flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, then immersing the whole body into zinc chloride solution containing 3 wt% of mass fraction for 700s, in the film forming process, generating ZIF in situ in the film by imidazole in the film casting solution and zinc chloride in a non-solvent, and preparing the PES-ZIF porous ion conduction film with the thickness of 63 mu m at 25 ℃. And soaking the prepared porous ion-conducting membrane in ethanol for 30 minutes, and drying at room temperature for 60 minutes, wherein in the drying process, the pore structure of the ZIF in the membrane pores can be kept unchanged, so that the collapse of the membrane pore structure is prevented. Soaking the membrane in 10 wt% dilute hydrochloric acid solution to remove ZIF generated in the membrane to obtain a PES porous ion-conducting membrane without ZIF, and applying the PES porous ion-conducting membrane in an all-vanadium flow battery at 80mA cm-2Under the working current density condition of (3), the coulombic efficiency of the battery is 97.85%, the voltage efficiency is 85.43%, and the energy efficiency is 83.59%.
Example 4
PES/imidazole is taken as a base material, and the PES/imidazole is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 26%, wherein the mass ratio of PES to imidazole is 8: 2, pouring the blending solution on a clean and flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, then immersing the whole body into zinc chloride solution containing 3 wt% of mass fraction for 700s, in the film forming process, generating ZIF in situ in the film by imidazole in the film casting solution and zinc chloride in a non-solvent, and preparing the PES-ZIF porous ion conduction film with the thickness of 63 mu m at 25 ℃. Soaking the prepared porous ion-conducting membrane in ethanol for 30 min, and drying at 70 deg.C for 60 min, although ZIF in the pores of the membrane can be maintainedThe pore structure of the porous ion-conducting membrane is kept unchanged, but due to overhigh drying temperature, the porous ion-conducting membrane shrinks violently, and the collapse of the pore structure is serious. Thus, after the membrane is soaked in a 10 wt% dilute hydrochloric acid solution to remove the generated ZIF in the membrane, a PES porous ion-conducting membrane without the ZIF is obtained and is used in an all-vanadium flow battery at 80mA cm-2Under the condition of working current density, the coulombic efficiency of the battery is 99.17%, the voltage efficiency is only 77.16%, and the energy efficiency is 76.52%.
Example 5
PES/imidazole is taken as a base material, and the PES/imidazole is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 26%, wherein the mass ratio of PES to imidazole is 8: 2, pouring the blending solution on a clean and flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, then immersing the whole body into zinc chloride solution containing 3 wt% of mass fraction for 700s, in the film forming process, generating ZIF in situ in the film by imidazole in the film casting solution and zinc chloride in a non-solvent, and preparing the PES-ZIF porous ion conduction film with the thickness of 63 mu m at 25 ℃. And soaking the prepared porous ion-conducting membrane in ethanol for 30 minutes, and drying at room temperature for 8 hours, wherein in the drying process, although the pore structure of the ZIF in the membrane pores can be kept unchanged, the porous ion-conducting membrane is seriously shrunk and seriously collapsed due to overlong drying time. Thus, after the membrane is soaked in a 10 wt% dilute hydrochloric acid solution to remove the generated ZIF in the membrane, a PES porous ion-conducting membrane without the ZIF is obtained and is used in an all-vanadium flow battery at 80mA cm-2Under the condition of the working current density, the coulombic efficiency of the battery is 99.67%, the voltage efficiency is only 82.29%, and the energy efficiency is 82.02%.
Comparative example 1 (conventional phase inversion method for directly preparing porous ion-conducting Membrane)
PES/PVP is used as a base material, and the PES/PVP is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 30%, wherein the mass ratio of the PES to the PVP is 9: 1, pouring the blended solution on a clean flat glass plate, volatilizing the solvent for 10s under the condition of 20% humidity, then immersing the whole body in water for 700s, and preparing a PES-PVP porous ion-conducting membrane (shown by a M3 table) at 25 DEG CShown). The catalyst is used in an all-vanadium flow battery at 80mA cm-2Under the operating current density condition of (2), the coulombic efficiency of the battery is 85.00%, the voltage efficiency is 86.84%, and the energy efficiency is 73.81% (fig. 2).
Comparative example 2
PES/PVP is used as a base material, and the PES/PVP is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 30%, wherein the mass ratio of PES to PVP is 9: pouring the blended solution on a clean flat glass plate, volatilizing the solvent for 10s under the humidity condition of 20%, immersing the whole body in water for 700s, preparing a PES-PVP porous ion-conducting membrane at 25 ℃, immersing the membrane in ethanol for 30 minutes at room temperature, and then drying for 2 hours at room temperature (expressed by M4). The catalyst is used in an all-vanadium flow battery at 80mA cm-2Under the condition of working current density, because the aperture of the prepared porous ion-conducting membrane is not large enough, the pore structure of the skin layer of the membrane is collapsed in the drying treatment process (figure 1), the membrane resistance is increased, and the all-vanadium redox flow battery assembled by the membrane cannot be charged and discharged normally (figure 2).
Comparative example 3 (secondary pore-forming of the film skin layer by adding pore-forming agent)
PES/PVP is used as a base material, calcium carbonate is used as a heterogeneous pore-forming agent, PES/PVP is dissolved in a DMAC solvent to obtain a heterogeneous blending solution with the mass concentration of 30%, calcium carbonate insoluble in DMAc is dispersed in the solution, and the mass ratio of PES to PVP is 9: 1, the mass ratio of PVP to calcium carbonate is 1: pouring the blended solution on a clean and flat glass plate, volatilizing the solvent for 10s under the condition of 20% humidity, immersing the whole body in water for 700s, preparing a PES-PVP-calcium carbonate porous ion-conducting membrane with the thickness of 78 mu m at 25 ℃, placing the membrane in 10 wt% hydrochloric acid solution to remove calcium carbonate in the membrane, placing the membrane in ethanol for soaking for 30 minutes at room temperature, and then drying for 2 hours at room temperature. The catalyst is used in an all-vanadium flow battery at 80mA cm-2Under the condition of working current density, the all-vanadium redox flow battery assembled by the all-vanadium redox flow battery cannot be charged and discharged normally due to large membrane resistance.
Comparative example 4
PES/PVP is taken as a base material, phenolphthalein isAnd (2) dissolving PES/PVP and phenolphthalein in a DMAC solvent to obtain a homogeneous blending solution with the high molecular weight concentration of 30%, wherein the mass ratio of PES to PVP is 9: 1, the mass ratio of PVP to phenolphthalein is 1: pouring the blended solution on a clean and flat glass plate, volatilizing the solvent for 10s under the condition of 20% humidity, immersing the whole body in water for 700s, preparing a PES-PVP-phenolphthalein porous ion-conducting membrane with the thickness of 66 mu m at 25 ℃, soaking the membrane in ethanol at room temperature for 24 hours to fully remove phenolphthalein in the membrane, and then drying at room temperature for 2 hours. The catalyst is used in an all-vanadium flow battery at 80mA cm-2Under the condition of working current density, the all-vanadium redox flow battery assembled by the all-vanadium redox flow battery still cannot be charged and discharged normally due to large membrane resistance.
Comparative example 5
PES/(PVP + imidazole) is taken as a base material, the PES/(PVP + imidazole) is dissolved in a DMAC solvent to obtain a blending solution with the mass concentration of 30%, wherein the mass ratio of the PES to the PVP is 9: 1, the mass ratio of PVP to imidazole is 1: 1; pouring the blended solution on a clean and flat glass plate, volatilizing the solvent for 10s under the condition of 20% humidity, then immersing the whole body in water for 700s, preparing a PES-PVP-imidazole porous ion conduction membrane (part of PVP and imidazole are dissolved in water in the process of membrane formation) with the thickness of 70 mu m at 25 ℃, then placing the membrane in ethanol for soaking for 30 minutes at room temperature, and then drying for 2 hours at room temperature. The catalyst is used in an all-vanadium flow battery at 80mA cm-2Under the condition of working current density, the coulombic efficiency of the battery is 99.76%, the voltage efficiency is 60.31%, and the energy efficiency is 60.17%. The main reasons are as follows: in the film forming process, the water solution does not contain zinc ions, the pore structure of the film is not supported by ZIF, and the pore structure collapses in the drying process, so that the ion selectivity of the film is greatly improved, and the ion conductivity is obviously reduced, namely, the battery has high coulombic efficiency and low voltage efficiency.

Claims (12)

1. A preparation method of an organic framework copolymer supported porous ion-conducting membrane is characterized by comprising the following steps:
(1) dissolving a high molecular resin raw material and a soluble organic skeleton copolymer precursor A in an organic solvent to form a homogeneous solution, and then uniformly coating the homogeneous solution on a substrate; volatilizing the solvent for 0-60 s under the condition that the relative humidity is 0-50%;
the organic framework copolymer precursor A is as follows: one or more of imidazole, methyl imidazole, 4, 5-dicarboxylimidazole, 4-hydroxymethyl imidazole hydrochloride, imidazole-4-ethyl formate, imidazole-4-methyl formate and 1H-imidazole-4-carboxylic acid;
(2) putting the matrix containing the homogeneous solution into a non-solvent containing an organic framework copolymer precursor B, and performing phase inversion to obtain a porous ion conduction membrane containing an organic framework copolymer support;
the organic framework copolymer precursor B in the step (2) is as follows: one or more of zinc chloride, zinc bromide, zinc acetate, zinc sulfate and zinc nitrate;
(3) treating the porous ion conducting membrane supported by the organic skeleton copolymer and drying; the membrane treatment method comprises the steps of soaking the ion-conducting membrane prepared in the step (2) in a non-solvent for at least 10 minutes, and drying at room temperature-80 ℃ for at least 5 minutes;
(4) and (4) placing the membrane subjected to drying treatment in the step (3) in an acid solution to remove the organic framework copolymer in the membrane pores, so as to obtain the porous ion-conducting membrane with a complete pore structure.
2. The method of claim 1, wherein: the polymer resin raw material in the step (1) is composed of a first polymer resin or a mixture of the first polymer resin and a second polymer resin:
the first type of polymer resin is composed of one or more than two of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyether ketone, polytetrafluoroethylene, polyvinylidene fluoride, polybenzimidazole, polyolefin and chloromethylated polysulfone;
the second type of polymer resin is formed by mixing one or more than two of water-soluble polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and polyquaternary ammonium salt;
wherein the first polymer resin is 100-40% of the mass content of the polymer resin raw material.
3. The method of claim 2, wherein: the first type of polymer resin is 95-65% of the mass content of the polymer resin raw material.
4. The method of claim 1, wherein: the organic skeleton copolymer precursor A in the raw materials in the step (1) accounts for 1-35% of the mass of the high polymer resin raw materials.
5. The production method according to claim 1, 2 or 4, characterized in that: the organic solvent in the step (1) is one or more of dimethyl sulfoxide (DMSO), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF); the mass concentration of the polymer resin raw material in the organic solvent is 26-40%.
6. The method of claim 1, wherein: the mass concentration of the organic skeleton copolymer precursor B in the non-solvent in the step (2) is 0.5-30%.
7. The production method according to claim 1 or 6, characterized in that: the non-solvent in the step (2) is water or alcohol CnH2n+2O, ketones CnH2nO and alkanes CnH2n+2One or more than two of (A), wherein CnH2n+2N in O is a positive integer of 1-6, ketone CnH2nN in O is a positive integer of 3-8 and alkanes CnH2n+2And n is a positive integer of 5-10.
8. The preparation method according to claim 1, wherein the temperature of the treatment method of the film in the step (3) is room temperature to 60 ℃; the drying time is 30-120 minutes.
9. The method of claim 1, wherein: the acidic solution in the step (4) is as follows: one or more than two of acetic acid solution, hydrochloric acid solution, sulfuric acid solution, methanesulfonic acid solution, phosphoric acid solution and nitric acid solution; wherein the acid concentration is 1-30 wt%.
10. The method of claim 9, wherein: the acid concentration is 5-20 wt%.
11. A porous ion-conducting membrane obtained by the preparation of the preparation process according to any one of claims 1 to 10.
12. Use of the porous ion-conducting membrane of claim 11 in a flow battery.
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