CN115000477A - Proton exchange membrane and preparation method and application thereof - Google Patents
Proton exchange membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a proton exchange membrane and a preparation method and application thereof, wherein the proton exchange membrane comprises, by mass, 100 parts of sulfonated polyether ether ketone, 3-20 parts of ionic liquid and 1-5 parts of covalent organic framework material. The proton exchange membrane has good proton conductivity and vanadium resistance, and has the advantages of high energy efficiency, good stability and the like when being applied to the all-vanadium redox flow battery.
Description
Technical Field
The invention relates to the field of all-vanadium redox flow batteries, in particular to a proton exchange membrane and a preparation method and application thereof.
Background
The all-vanadium redox flow battery is a clean and efficient battery and is considered to be a green energy storage battery with the greatest application prospect. The proton exchange membrane is an important component of the all-vanadium redox flow battery, but the proton exchange membrane in the prior art cannot give consideration to both ion conduction performance and vanadium resistance performance, so that the development of the all-vanadium redox flow battery is restricted.
At present, the ionic liquid has good ionic conductivity and vanadium resistance, and is a good modified material of a proton exchange membrane. Patent document CN102437349A discloses an ionic liquid reinforced membrane for an all-vanadium redox flow battery and a preparation method thereof, wherein the ionic liquid is supported on a polymer to improve the vanadium resistance of the ionic liquid reinforced membrane. However, the proton exchange membrane obtained by blending the ionic liquid and the polymer matrix has poor stability, and the ionic liquid is easy to lose in the long-term use process, so that the performance of the proton exchange membrane is reduced.
Therefore, how to maximize the advantages of the ionic liquid and make the proton conductivity and vanadium resistance of the proton exchange membrane have continuously excellent performances in a long-term use process is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a proton exchange membrane which has good proton conductivity, vanadium resistance and stability.
The invention also provides a preparation method of the proton exchange membrane, which can be used for preparing the proton exchange membrane and has the advantages of simple preparation process, easy operation and the like.
The invention also provides an all-vanadium redox flow battery which adopts the proton exchange membrane and has the advantages of high energy efficiency, good stability and the like.
The proton exchange membrane comprises, by mass, 100 parts of sulfonated polyether ether ketone, 3-20 parts of ionic liquid and 1-5 parts of covalent organic framework material.
According to one embodiment of the invention, the degree of sulfonation of the sulfonated polyetheretherketone is from 45 to 75%.
According to one embodiment of the present invention, the ionic liquid comprises at least one of 1-ethyl-3-methylimidazolium methane sulfonate, 1-ethyl-3-methylimidazolium ethyl sulfate, and 1-butyl-3-methylimidazolium tetrafluoroborate.
According to one embodiment of the present invention, the covalent organic framework material is prepared from an amino monomer and trialdehyde phloroglucinol in the presence of a catalyst, wherein the amino monomer comprises at least one of p-phenylenediamine, 2, 5-diaminobenzenesulfonic acid and 2, 5-diaminopyridine.
According to one embodiment of the present invention, the molar ratio of amino monomer to trialdehyde phloroglucinol is (1-3): 2.
according to one embodiment of the invention, the molar ratio of amino monomer to catalyst is 1: (5-15); the catalyst comprises at least one of acetic acid and p-toluenesulfonic acid.
In a second aspect of the present invention, a method for preparing the proton exchange membrane is provided, including: (1) sequentially adding ionic liquid dispersion liquid and sulfonated polyether-ether-ketone solution into the covalent organic framework material, and uniformly mixing to prepare film forming liquid; (2) and carrying out film forming treatment on the film forming solution to obtain the proton exchange membrane.
According to an embodiment of the present invention, the step (1) includes: firstly, carrying out vacuum treatment on a covalent organic framework at 100 ℃ for 1h-3h, then mixing the covalent organic framework with ionic liquid dispersion liquid, carrying out vacuum treatment at 80 ℃ for 1h-3h, then adding a sulfonated polyether-ether-ketone solution into the covalent organic framework, and uniformly mixing to obtain a film-forming liquid.
According to an embodiment of the present invention, the mass concentration of the sulfonated polyetheretherketone solution is 18% to 20%, and the solvent in the sulfonated polyetheretherketone solution comprises at least one of dimethylsulfoxide, dimethylformamide, and dimethylacetamide.
The third aspect of the invention provides an all-vanadium redox flow battery, which comprises the proton exchange membrane or the proton exchange membrane prepared by the preparation method.
The implementation of the invention has at least the following beneficial effects:
the proton exchange membrane provided by the invention has higher proton conductivity, has the advantages of good vanadium resistance, stability and the like, effectively overcomes the defects of weak interaction force between ionic liquid and polymer, easy loss of the ionic liquid, poor proton conductivity, poor stability and the like of the proton exchange membrane in the prior art, and has important practical significance in industry.
The preparation method of the proton exchange membrane provided by the invention has the characteristics of good proton conductivity, stability, vanadium resistance and the like, is simple in preparation process, easy to operate, mild in condition, free of harsh conditions such as high temperature and the like, low in cost, environment-friendly and beneficial to actual industrial production and application.
The all-vanadium redox flow battery provided by the invention has the advantages of high energy efficiency, long stability and the like by adopting the proton exchange membrane.
Drawings
FIG. 1 is a graph showing the energy efficiency of proton exchange membranes of examples of the present invention and comparative examples at different current densities;
FIG. 2 is a graph showing the current density of 100mA/cm for proton exchange membranes of examples and comparative examples of the present invention 2 Cycling stability of time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a proton exchange membrane which comprises, by mass, 100 parts of sulfonated polyether ether ketone, 3-20 parts of ionic liquid and 1-5 parts of covalent organic framework material.
The proton exchange membrane provided by the invention takes sulfonated polyether ether ketone as a polymer matrix, and simultaneously introduces ionic liquid and covalent organic framework material (COF), so that the proton exchange membrane has good proton conductivity and vanadium resistance.
The inventor has considered through research and analysis that, on one hand, COF is a porous material, and the porous structure of COF is favorable for constructing effective proton channels, so that the proton exchange membrane shows excellent proton conductivity; on the other hand, functional groups forming the COF can generate ionic bonds with ionic liquid, and the porous structure of the COF is also beneficial to the capture of the ionic liquid, so that the ionic liquid can be firmly loaded in the pore channels of the COF under the dual actions of the ionic bonds and the porous structure, and the long-term effective improvement of proton conductivity and vanadium resistance of the proton exchange membrane by the ionic liquid is realized.
In addition, under the raw material composition system of the proton exchange membrane, COF loaded with ionic liquid is uniformly dispersed in a sulfonated polyetheretherketone matrix, so that the proton exchange membrane has more balanced performance in proton conductivity and vanadium resistance.
In some embodiments, the sulfonation degree of the sulfonated polyether ether ketone is 45% -75%, which is more beneficial to improving the proton conductivity and other properties of the proton exchange membrane. The sulfonation degree of the sulfonated polyether ether ketone refers to sulfo (-SO) in the sulfonated polyether ether ketone 3 ) The mass content of the sulfonated polyether ether ketone is adopted as the matrix of the proton exchange membrane, which is beneficial to improving the proton conductivity of the proton exchange membrane.
Further, the sulfonated polyether ether ketone may be a sulfonated product obtained by sulfonating polyether ether ketone with concentrated sulfuric acid. The molecular weight of the polyetheretherketone is not limited herein, and the polyetheretherketone of the present invention can be commercially available or can be prepared by conventional methods.
The imidazole ionic liquid has excellent vanadium resistance and proton conductivity. In some embodiments, the ionic liquid comprises at least one of 1-ethyl-3-methylimidazolium methane sulfonate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-butyl-3-methylimidazolium tetrafluoroborate.
The inventor considers through research and analysis that the ionic liquid has the advantage of high ionic conductivity, and the proton conductivity of the proton exchange membrane is further improved by doping the ionic liquid into the proton exchange membrane; in addition, the imidazole cation of the ionic liquid has a Tangnan effect on vanadium ions, and the ionic liquid is doped into the proton exchange membrane, so that the vanadium ions of the proton exchange membrane are effectively inhibited from permeating and migrating.
In the present invention, the covalent organic framework material specifically includes ketoenamine covalent organic framework materials. In a preferred embodiment, the covalent organic framework material is prepared from an amino monomer and trialdehyde phloroglucinol under the action of a catalyst.
Specifically, the amino monomer comprises at least one of p-phenylenediamine, 2, 5-diaminobenzenesulfonic acid and 2, 5-diaminopyridine, and the COF synthesized by the amino monomer and trialdehyde phloroglucinol is a ketoenamine covalent organic framework material.
In the above examples, the amino monomer, the trialdehyde phloroglucinol, and the first solvent are mixed to form a mixture; carrying out ultrasonic treatment on the mixture for 10min-30min to uniformly mix the mixture; and (3) carrying out vacuum treatment at 90-120 ℃ for 48-72 h, collecting a reaction product, repeatedly washing the reaction product, and drying to obtain the COF.
Specifically, the mixture after ultrasonic treatment is placed in a reaction container for reaction, the reaction container is frozen by liquid nitrogen, the reaction container is vacuumized by a vacuum pump after the mixture is completely solidified, and then the mixture is subjected to vacuum treatment for 48 to 72 hours at the temperature of between 90 and 120 ℃.
Specifically, in the above mixture, the molar ratio of the amino monomer to the trialdehyde phloroglucinol may be (1-3): 2, the performance of the synthesized proton exchange membrane is facilitated.
Further, the amount of the first solvent may be controlled as: the mass-volume ratio of the amino monomer to the first solvent is 1 g: 40mL-100mL, and the first solvent specifically includes water, dioxane, and m-trimethylbenzene, but is not limited thereto.
In some embodiments, the molar ratio of the amino monomer to the catalyst may be 1: (5-15) for the catalytic synthesis of COF. Specifically, the catalyst comprises at least one of acetic acid and p-toluenesulfonic acid.
The preparation method of the proton exchange membrane provided by the invention comprises the following steps:
(1) sequentially adding ionic liquid dispersion liquid and sulfonated polyether-ether-ketone solution into the covalent organic framework material, and uniformly mixing to prepare film forming liquid;
(2) and performing film forming treatment on the film forming solution to obtain the proton exchange membrane.
The preparation method of the proton exchange membrane provided by the invention can be used for preparing the proton exchange membrane with the characteristics of good proton conductivity, stability, vanadium resistance and the like, and has the advantages of simple preparation process, easiness in operation, mild condition, no need of harsh conditions such as high temperature and the like, low cost, environmental friendliness and contribution to practical industrial production and application.
In some embodiments, step (1) comprises: and (2) mixing the covalent organic framework material with the ionic liquid dispersion liquid, carrying out vacuum treatment for 1-3 h at the temperature of 80 ℃, adding a sulfonated polyether-ether-ketone solution into the mixture, and uniformly mixing to obtain a film forming liquid.
In the above embodiment, after the mixed solution of the covalent organic framework material and the ionic liquid dispersion liquid is processed under vacuum condition, the ionic liquid is loaded on the covalent organic framework material, and then the sulfonated polyether ether ketone solution is added to the covalent organic framework material loaded with the ionic liquid, so that the ionic liquid and the covalent organic framework material are loaded on the sulfonated polyether ether ketone under the interaction between the covalent organic framework material and the sulfonated polyether ether ketone.
The covalent organic framework material is generally processed for 1h to 3h under the vacuum condition of 100 ℃ so as to realize the activation of the covalent organic framework material.
The ionic liquid dispersion of the present invention can be obtained by a conventional method, for example, by dissolving an ionic liquid in a solvent (hereinafter referred to as a second solvent) at room temperature to form the ionic liquid dispersion; wherein the second solvent may include at least one of dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), and dimethylacetamide (DMAc). The mass to volume ratio of ionic liquid to second solvent may generally be from 0.45g to 3 g: 10mL, e.g., 0.45 g: 10mL, 0.75 g: 10mL, 0.8 g: 10mL, 1 g: 10mL, 2 g: 10mL, 3 g: 10mL or any two thereof, and the like.
In the sulfonated polyether ether ketone solution, the mass concentration (mass percentage) of the sulfonated polyether ether ketone may be generally 18% to 20%, for example, 18%, 18.5%, 19%, 19.5%, 20%, or a range composed of any two of these values, and in the specific operation, the sulfonated polyether ether ketone may be dissolved in a solvent (hereinafter referred to as a third solvent) at room temperature to form the sulfonated polyether ether ketone solution; wherein the third solvent may include at least one of dimethyl sulfoxide (DMSO), Dimethylformamide (DMF), and dimethylacetamide (DMAc).
In the above production process, the film formation treatment may generally include: coating the film-forming solution on a substrate, removing bubbles, and removing the solvent to obtain the proton exchange membrane; wherein, the solvent can be removed by vacuum drying, etc., and the drying temperature can be generally 50-100 deg.C, and further 50-90 deg.C, such as 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, or any two ranges thereof; in the specific implementation, a glass plate, a stainless steel substrate or other conventional substrates in the art can be used, the invention is not limited to the coating method, and the proton exchange membrane can be obtained by casting the deposition solution onto the substrate by a casting method and then removing the solvent.
The all-vanadium redox flow battery provided by the invention comprises the proton exchange membrane or the proton exchange membrane prepared by the preparation method. The proton exchange membrane provided by the invention not only can keep good proton conductivity, but also can effectively inhibit the performance reduction of the battery caused by the permeation and migration of vanadium ions, thereby improving the energy efficiency and the service life of the battery.
Except for the proton exchange membrane, the structure of the all-vanadium redox flow battery can be the structure of the conventional all-vanadium redox flow battery in the field, and redundant description is omitted.
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Mixing 0.126g of trialdehyde phloroglucinol, 0.169g of 2, 5-diaminobenzene sulfonic acid, 1.2mL of dioxane, 4.8mL of m-trimethylbenzene and 1.2mL of acetic acid solution to obtain a mixture, carrying out ultrasonic treatment for 10min, placing the mixture after ultrasonic treatment in a reaction container for reaction, freezing the reaction container by using liquid nitrogen, vacuumizing the reaction container by using a vacuum pump after the mixture is completely solidified, and carrying out vacuum treatment at 120 ℃ for 72h to obtain the covalent organic framework material (TpPa-SO) 3 H) (ii) a Wherein the concentration of the acetic acid solution is 6 moL/L;
(2) dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-butyl-3-methylimidazolium tetrafluoroborate in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
placing 0.009g of covalent organic framework in a vacuum oven at 100 ℃ for processing for 2h, then sequentially dropwise adding 200 μ L of ionic liquid dispersion liquid for vacuum processing at 80 ℃ for 1h, then adding 1.5g of sulfonated polyether ether ketone solution with the mass fraction of 20% into the ionic liquid dispersion liquid, and stirring the mixture at room temperature for 24h to prepare a film forming solution;
(3) dripping the formed film on the surface of a stainless steel substrate, uniformly coating by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles in a vacuum environment at 50 ℃, and performing vacuum treatment for 72 hours at 80 ℃ to obtain a proton exchange membrane;
0.045g of proton exchange membrane is soaked in 20mL of deionized water at 25 ℃ for 10d, the concentration of boron in the soaking solution is tested by adopting an inductively coupled plasma emission spectrometer, and the loss of the ionic liquid is reflected by the concentration of the boron.
Example 2
(1) Mixing 0.126g of trialdehyde phloroglucinol, 0.169g of 2, 5-diaminobenzene sulfonic acid, 1.2mL of dioxane, 4.8mL of m-trimethylbenzene and 1.2mL of acetic acid solution to obtain a mixture, carrying out ultrasonic treatment for 10min, placing the mixture after ultrasonic treatment in a reaction container for reaction, and placing the reaction container for reactionFreezing with liquid nitrogen, vacuumizing the reaction container with a vacuum pump after the mixture is completely solidified, and performing vacuum treatment at 120 deg.C for 72 hr to obtain covalent organic framework material (TpPa-SO) 3 H) (ii) a Wherein the concentration of the acetic acid solution is 6 moL/L;
(2) dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 45%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-butyl-3-methylimidazolium tetrafluoroborate in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
placing 0.009g of covalent organic framework in a vacuum oven at 100 ℃ for processing for 2h, then sequentially dropwise adding 200 mu L of ionic liquid dispersion liquid for vacuum processing at 80 ℃ for 1h, then adding 1.5g of sulfonated polyether ether ketone solution with the mass fraction of 20 percent, stirring at room temperature for 24h, and preparing a film forming solution;
(3) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles in a vacuum environment at 50 ℃, and performing vacuum treatment for 72 hours at 80 ℃ to obtain the proton exchange membrane.
Example 3
(1) Mixing 0.126g of trialdehyde phloroglucinol, 0.169g of 2, 5-diaminobenzene sulfonic acid, 0.086g of p-toluenesulfonic acid, 1.2mL of dioxane and 4.8mL of m-trimethylbenzene, carrying out ultrasonic treatment for 10min, placing the mixture after ultrasonic treatment in a reaction container for reaction, freezing the reaction container by using liquid nitrogen, vacuumizing the reaction container by using a vacuum pump after the mixture is completely solidified, and carrying out vacuum treatment at 120 ℃ for 72h to obtain the covalent organic framework material (TpPa-SO) 3 H)；
(2) Dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-butyl-3-methylimidazolium tetrafluoroborate in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
placing 0.009g of covalent organic framework in a vacuum oven at 100 ℃ for processing for 2h, then sequentially dropwise adding 200 μ L of ionic liquid dispersion liquid for vacuum processing at 80 ℃ for 1h, then adding 1.5g of sulfonated polyether ether ketone solution with the mass fraction of 20% into the ionic liquid dispersion liquid, and stirring the mixture at room temperature for 24h to prepare a film forming solution;
(3) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles in a vacuum environment at 50 ℃, and performing vacuum treatment for 72 hours at 80 ℃ to obtain the proton exchange membrane.
Example 4
(1) Mixing 0.126g of trialdehyde phloroglucinol, 0.098g of 2, 5-diaminopyridine, 1.2mL of dioxane, 4.8mL of m-trimethylbenzene and 1.2mL of acetic acid solution to obtain a mixture, carrying out ultrasonic treatment for 10min, placing the mixture subjected to ultrasonic treatment in a reaction container for reaction, freezing the reaction container by using liquid nitrogen, vacuumizing the reaction container by using a vacuum pump after the mixture is completely solidified, and carrying out vacuum treatment at 120 ℃ for 72h to obtain a covalent organic framework material (TpPa-Py); wherein the concentration of the acetic acid solution is 6 moL/L;
(2) dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-butyl-3-methylimidazolium tetrafluoroborate in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
placing 0.009g of covalent organic framework in a vacuum oven at 100 ℃ for processing for 2h, then sequentially dropwise adding 200 μ L of ionic liquid dispersion liquid for vacuum processing at 80 ℃ for 1h, then adding 1.5g of sulfonated polyether ether ketone solution with the mass fraction of 20% into the ionic liquid dispersion liquid, and stirring the mixture at room temperature for 24h to prepare a film forming solution;
(3) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles in a vacuum environment at 50 ℃, and performing vacuum treatment for 72 hours at 80 ℃ to obtain the proton exchange membrane.
Example 5
(1) Mixing 0.126g trialdehyde phloroglucinol, 0.169g 2, 5-diaminobenzene sulfonic acid, 1.2mL dioxane, 4.8mL m-trimethylbenzene, and 1.2mL acetic acid solution to obtain a mixture, performing ultrasonic treatment for 10min, and mixing the above materialsPlacing the mixture after ultrasonic treatment in a reaction vessel for reaction, freezing the reaction vessel with liquid nitrogen, vacuumizing the reaction vessel by using a vacuum pump after the mixture is completely solidified, and performing vacuum treatment at 120 ℃ for 72 hours to obtain a covalent organic framework material (TpPa-SO) 3 H) (ii) a Wherein the concentration of the acetic acid solution is 6 moL/L;
(2) dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-ethyl-3-methylimidazol ethyl sulfate salt in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
placing 0.009g of covalent organic framework in a vacuum oven at 100 ℃ for processing for 2h, then sequentially dropwise adding 200 μ L of ionic liquid dispersion liquid for vacuum processing at 80 ℃ for 1h, then adding 1.5g of sulfonated polyether ether ketone solution with the mass fraction of 20% into the ionic liquid dispersion liquid, and stirring the mixture at room temperature for 24h to prepare a film forming solution;
(3) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles in a vacuum environment at 50 ℃, and performing vacuum treatment for 72 hours at 80 ℃ to obtain the proton exchange membrane.
Comparative example 1
(1) Dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare a sulfonated polyether ether ketone solution, and stirring at room temperature for 24 hours to obtain a uniformly dispersed film forming solution;
(2) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles at 50 ℃ in a vacuum environment, and performing vacuum treatment at 80 ℃ for 72 hours to obtain the proton exchange membrane.
Comparative example 2
(1) Dissolving 0.3g of sulfonated polyether ether ketone (sulfonation degree: 60%) in 1.2g of dimethyl sulfoxide solvent to prepare sulfonated polyether ether ketone solution, dissolving 0.75g of 1-butyl-3-methylimidazolium tetrafluoroborate in 10mL of dimethyl sulfoxide solvent, and performing ultrasonic treatment for 30min to obtain ionic liquid dispersion liquid;
mixing 200 mu L of ionic liquid dispersion liquid and sulfonated polyether-ether-ketone solution, and stirring at room temperature for 24h to obtain uniformly dispersed film forming liquid;
(2) dripping the formed film on the surface of a stainless steel substrate, coating at a constant speed by adopting a film coater with the specification of 600 mu m to obtain a uniform and transparent liquid film, removing bubbles at the temperature of 50 ℃ in a vacuum environment, and performing vacuum treatment at the temperature of 80 ℃ for 72 hours to obtain a proton exchange membrane;
0.045g of proton exchange membrane is soaked in 20mL of deionized water at 25 ℃ for 10d, the concentration of boron in the soaking solution is tested by adopting an inductively coupled plasma emission spectrometer, and the loss of the ionic liquid is reflected by the concentration of the boron.
Comparative example 3
Pretreating a Nafion115 membrane to obtain a proton exchange membrane, wherein the pretreatment comprises the following steps: the Nafion115 membrane was soaked in 3 wt% H 2 O 2 Treating the solution at 60 ℃ for 1h, taking out a sample, and washing the surface with deionized water; then placed in H of 1moL/L 2 SO 4 Treating in the solution at 60 deg.C for 1 h; finally, taking out the sample and placing the sample in deionized water at 60 ℃ for treatment for 1 h.
The proton exchange membranes of examples 1 to 2 and comparative examples 1 to 5 were used as test samples to conduct the following performance tests, and the test results are shown in table 1, table 2, fig. 1, and fig. 2.
1. Determination of energy efficiency
Cutting the proton exchange membrane into a sample with the specification of 30mm multiplied by 30mm, and soaking the sample in deionized water at room temperature for 24 h;
the soaked sample is used as a proton exchange membrane of a vanadium redox flow battery, wherein the vanadium redox flow battery comprises a positive electrode, a negative electrode and a proton exchange membrane arranged between the negative electrodes, and the electrolyte of the positive electrode and the negative electrode is 20mL and 1.5 mol.L –1 V 3.5+ 3 mol. L of –1 H 2 SO 4 A solution; the positive electrode and the negative electrode are made of graphite felt active materials, and the effective area is 4cm 2 Respectively at 40mA/cm 2 、60mA/cm 2 、80mA/cm 2 、100mA/cm 2 、120mA/cm 2 The energy efficiency of the cell was tested at a current density of 100mA/cm 2 The cells were tested for cycle energy efficiency 60 times.
2. Determination of vanadium ion permeability
Cutting the proton exchange membrane into a sample with the specification of 15mm multiplied by 15mm, and soaking the sample in deionized water at room temperature for 24 h;
the vanadium ion permeability test is carried out in a diffusion cell sandwiched with a proton exchange membrane. The left side of the diffusion pool is 7mL of vanadyl sulfate solution, and the left side of the diffusion pool is 7mL of magnesium sulfate solution, wherein the concentrations of the vanadyl sulfate solution and the magnesium sulfate solution are both 1.5 moL/L; and testing the osmotic concentration of the vanadium ions on the left side of the diffusion cell by adopting an ultraviolet spectrophotometer method.
Vanadium ion permeability of the proton exchange membranes according to examples 1 to 5 and comparative examples 1 to 3 and 40mA/cm 2 The energy efficiency at current density of (a) is shown in table 1.
TABLE 1
| Numbering | Film thickness/. mu.m | Permeability of vanadium ion/10 -7 ·cm 2 ·min -1 | Energy efficiency/%) |
| Example 1 | 55±2 | 2.47 | 91.7 |
| Example 2 | 56±1 | 1.86 | 85.9 |
| Example 3 | 54±1 | 2.53 | 90.0 |
| Example 4 | 57±1 | 2.27 | 88.9 |
| Example 5 | 52±1 | 2.67 | 90.4 |
| Comparative example 1 | 53±2 | 12.6 | 81.4 |
| Comparative example 2 | 51±1 | 3.92 | 88.0 |
| Comparative example 3 | 127±1 | 21.7 | 84.4 |
TABLE 2
| Numbering | Measured element | Content (mg/L) |
| Example 1 | Boron | 0.5967 |
| Comparative example 2 | Boron | 1.0242 |
FIG. 1 is a graph of examples 1-5 at 40mA/cm for the proton exchange membranes of comparative examples 1-3 2 、60mA/cm 2 、80mA/cm 2 、100mA/cm 2 、120mA/cm 2 The initial energy efficiency of the cell was tested at a current density of (1), and FIG. 2 is a graph showing that the proton exchange membranes of example 1 and comparative examples 1 to 3 had a current density of 100mA/cm 2 The cycle energy efficiency. As can be seen from fig. 1 and 2, the vanadium redox flow battery using the proton exchange membrane provided by the present invention has higher energy efficiency and cycle performance.
Table 2 shows the boron concentration in the leachate after soaking the proton exchange membrane of example 1 and comparative example 2 for 10 days. According to the table 1 and the table 2, the proton exchange membrane provided by the invention solves the problem of high loss rate of the ionic liquid, and the vanadium resistance of the proton exchange membrane provided by the invention is superior to that of a comparative example; meanwhile, as can be seen from fig. 1, when the proton exchange membrane of the invention is used in a vanadium flow battery, the energy efficiency and the cycle stability of the vanadium flow battery can be improved.
The above detailed description of the preferred embodiments of the present invention and experimental verification. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concept. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. The proton exchange membrane is characterized by comprising 100 parts by mass of sulfonated polyether ether ketone, 3-20 parts by mass of ionic liquid and 1-5 parts by mass of covalent organic framework material.
2. The proton exchange membrane according to claim 1, wherein the sulfonated polyetheretherketone has a sulfonation degree of 45-75%.
3. The proton exchange membrane according to claim 1, wherein the ionic liquid comprises at least one of 1-ethyl-3-methylimidazolium methane sulfonate, 1-ethyl-3-methylimidazolium ethyl sulfate, and 1-butyl-3-methylimidazolium tetrafluoroborate.
4. The proton exchange membrane according to claim 1, wherein the covalent organic framework material is prepared from an amino monomer and trialdehyde phloroglucinol in the presence of a catalyst, wherein the amino monomer comprises at least one of p-phenylenediamine, 2, 5-diaminobenzenesulfonic acid and 2, 5-diaminopyridine.
5. The proton exchange membrane according to claim 4, wherein the molar ratio of the amino monomer to the trialdehyde phloroglucinol is (1-3): 2.
6. the proton exchange membrane according to claim 4 wherein the molar ratio of the amino monomer to the catalyst is 1: (5-15); the catalyst comprises at least one of acetic acid and p-toluenesulfonic acid.
7. The process for the preparation of a proton exchange membrane according to any one of claims 1 to 6, comprising:
(1) sequentially adding ionic liquid dispersion liquid and sulfonated polyether-ether-ketone solution into the covalent organic framework material, and uniformly mixing to prepare film forming liquid;
(2) and carrying out film forming treatment on the film forming solution to obtain the proton exchange membrane.
8. The method according to claim 7, wherein the step (1) comprises: firstly, carrying out vacuum treatment on a covalent organic framework at 100 ℃ for 1h-3h, then mixing the covalent organic framework with the ionic liquid dispersion liquid, carrying out vacuum treatment at 80 ℃ for 1h-3h, then adding the sulfonated polyether-ether-ketone solution into the ionic liquid dispersion liquid, and uniformly mixing to obtain a film forming liquid.
9. The preparation method according to claim 7, wherein the mass concentration of the sulfonated polyetheretherketone solution is 18 to 20%, and the solvent in the sulfonated polyetheretherketone solution comprises at least one of dimethyl sulfoxide, dimethylformamide and dimethylacetamide.
10. An all-vanadium flow battery, which is characterized by comprising the proton exchange membrane of any one of claims 1 to 6 or the proton exchange membrane prepared by the preparation method of any one of claims 7 to 9.
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| CN117638127A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
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| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN114213670A (en) * | 2021-12-28 | 2022-03-22 | 河北科技大学 | Ionic covalent organic framework material, preparation method and application thereof, and lithium metal negative electrode material |
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| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
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Cited By (2)
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| CN117638127A (en) * | 2024-01-26 | 2024-03-01 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
| CN117638127B (en) * | 2024-01-26 | 2024-04-26 | 杭州德海艾科能源科技有限公司 | High-ion-selectivity mixed matrix porous diaphragm for vanadium battery and preparation method thereof |
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