Gel polymer electrolyte diaphragm and preparation method thereof and zinc ion battery

Abstract

The present invention provides a method for preparing a gel polymer electrolyte membrane, comprising the following steps: blending a two-dimensional polymer carboxylate with a hydrophilic monomer, adding a cross-linking agent and a first initiator thereto, and reacting under light conditions to obtain a film; dialyzing and soaking the film to obtain a gel polymer electrolyte membrane; the two-dimensional polymer carboxylate preparation method is as follows: subjecting 3,5-diaminobenzoic acid and acryloyl chloride to a substitution reaction to obtain a monomer DBA; subjecting p-aminobenzoic acid and acryloyl chloride to a substitution reaction to obtain a monomer ADA; mixing the monomers DBA and ADA, adding an organic base and a second initiator thereto, and performing a polymerization reaction to obtain the two-dimensional polymer carboxylate. The present invention generates a gel polymer electrolyte membrane by blending the synthesized two-dimensional polymer carboxylate with the hydrophilic monomer. The introduction of the two-dimensional polymer carboxylate brings about stronger ionic interactions, thereby improving the mechanical properties of the membrane.

Description

Technical Field

[0001] The present application relates to the field of battery technology, and in particular to a gel polymer electrolyte membrane and a preparation method thereof, and a zinc ion battery. Background Art

[0002] Zinc-ion batteries have attracted extensive research due to their inherent green safety, low price, and abundant reserves. The metallic zinc anode has a high theoretical capacity (820 mAh / g) and a lower redox potential (-0.76 V) than the standard hydrogen electrode. However, during the charge and discharge cycle, the zinc electrode is easily corroded, producing zinc dendrites and by-products produced by the hydrogen evolution reaction, resulting in reduced coulombic efficiency, shortened cycle life, and even battery short circuit. In addition, the problem of easy leakage of liquid electrolytes also poses a huge safety hazard, limiting its commercial application. To overcome these obstacles, people have developed a variety of strategies, such as optimizing the electrolyte composition, zinc anode surface coating, and constructing ion transfer channels. In addition, the design of new separators is also considered to be a simple but effective strategy to improve battery stability.

[0003] Glass fiber (GF) separator is the most commonly used separator in aqueous battery. However, most GF separators have large but uneven pores and lack zinc-philic groups. This is not conducive to the Zn 2+ The uniform distribution and desolvation of Zn lead to the crazy growth of Zn dendrites and the generation of hydrogen evolution reaction. To date, various modification strategies of GF membranes have been reported to protect the zinc anode. For example, a component with a large number of polar groups is introduced into the GF membrane to absorb Zn 2+ , which can avoid Zn 2+ Uneven deposition on the zinc anode surface inhibits the formation of zinc dendrites. Adding ion sieves with uniform micro / mesoporous ion channels to the GF separator can regulate zinc plating / stripping, thereby allowing zinc to be uniformly deposited on the anode. However, the above strategy fails to solve the inherent poor mechanical properties of the GF separator itself. Therefore, dendrite growth can easily puncture the separator, causing a short circuit in the battery.

[0004] Gel electrolyte (GPE) separators are one of the effective means to solve the above problems. Gel polymer electrolyte separators are a quasi-solid electrolyte separator composed of a hydrophilic polymer chain network and a saline solution. They not only have a solid structure similar to that of solid electrolytes, but also have higher ionic conductivity near aqueous electrolytes. Although GPE separators are superior to aqueous electrolytes in some aspects, they also have the following problems: the low ionic conductivity of GPE separators leads to their higher overpotential, the poor affinity with electrodes increases the interfacial impedance of the electrolyte-electrode interface, and the poor mechanical properties hinder their widespread application in wearable devices. Summary of the Invention

[0005] The technical problem to be solved by the present invention is how to improve the mechanical properties of gel electrolyte.

[0006] The present invention solves the above technical problems through the following technical means:

[0007] The first aspect of the present invention provides a method for preparing a gel polymer electrolyte membrane, comprising the following steps: blending a two-dimensional polymer carboxylate with a hydrophilic monomer, adding a crosslinker and a first initiator thereto, and reacting under light conditions to obtain a film; dialyzing and soaking the film to obtain a gel polymer electrolyte membrane; the method for preparing the two-dimensional polymer carboxylate is as follows: subjecting 3,5-diaminobenzoic acid to a substitution reaction with acryloyl chloride to obtain a monomer DBA; subjecting p-aminobenzoic acid to a substitution reaction with acryloyl chloride to obtain a monomer ADA; and mixing the monomers DBA and ADA, adding an organic base and a second initiator thereto to carry out a polymerization reaction to obtain the two-dimensional polymer carboxylate.

[0008] Beneficial effects: The two-dimensional polymer carboxylate synthesized by the present invention has a hydrophobic-hydrophilic layered structure and a high specific surface area; the present invention generates a gel polymer electrolyte membrane by blending the synthesized two-dimensional polymer carboxylate with a hydrophilic monomer. The introduction of the two-dimensional polymer carboxylate brings about stronger ionic interaction, improves the mechanical properties of the membrane, and at the same time brings about a certain self-healing ability. When the gel polymer electrolyte membrane is punctured by dendrites, it has a certain recovery ability; the present invention introduces the two-dimensional polymer carboxylate into the gel polymer electrolyte membrane, brings abundant carboxylate groups, can reduce the hydration degree of zinc ions, and effectively inhibit the hydrogen evolution reaction.

[0009] Preferably, the hydrophilic monomer includes a cationic monomer and an anionic monomer, the cationic monomer includes one of acryloyloxyethyltrimethylammonium chloride, acrylamidomethylpropanesulfonic acid and vinylpyridine; the anionic monomer includes one of sodium styrenesulfonate and 2-acrylamido-2-methylpropanesulfonic acid.

[0010] Beneficial effects: The present invention forms a long-range ordered anion and cation transfer channel through the functional group interaction between carboxylate, ammonium and sulfonate groups, which can achieve higher ion transport in the battery, improve ion conductivity, facilitate uniform ion deposition and inhibit the formation of dendrites; in addition, the introduced zinc-philic group carboxylate is conducive to the contact between the gel electrolyte and the zinc electrode, reducing the interface impedance of the electrolyte-electrode interface.

[0011] Preferably, the cross-linking agent includes one of divinylbenzene, diisocyanate and N,N-methylenebisacrylamide.

[0012] Preferably, the first initiator includes one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0013] Preferably, the organic base is 1,1,3,3-tetramethylguanidine; and the second initiator is potassium persulfate.

[0014] Preferably, the cross-linking agent accounts for 0.5% of the mass of the hydrophilic monomer.

[0015] Preferably, the first initiator accounts for 0.8% of the mass of the hydrophilic monomer.

[0016] Preferably, the illumination condition is ultraviolet light with a wavelength of 365 nm.

[0017] A second aspect of the present invention provides a gel polymer electrolyte membrane, which is prepared according to the above-mentioned method for preparing a gel polymer electrolyte membrane.

[0018] Beneficial effects: The gel polymer electrolyte membrane of the present invention has good mechanical properties, high ionic conductivity, good anion and cation transfer channels and certain self-healing ability, which can improve the battery cycle life; the functional groups in the gel polymer electrolyte membrane have a strong interaction force with water, which reduces the hydration degree of zinc ions, effectively inhibits the hydrogen evolution reaction, and improves the battery cycle life.

[0019] A third aspect of the present invention provides a zinc ion battery comprising a positive electrode, a separator and a negative electrode, wherein the separator is the gel polymer electrolyte separator. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the monomer DBA in the embodiment;

[0021] Figure 2 This is the hydrogen nuclear magnetic resonance spectrum of monomer ADA in the embodiment;

[0022] Figure 3 is a hydrogen nuclear magnetic resonance spectrum of a two-dimensional polymer carboxylate in the embodiment;

[0023] Figure 4 1 is a stress-strain curve of the gel polymer electrolyte membrane of Example 1, the electrolyte membrane of Comparative Example 1, and the commercial membrane of Comparative Example 2, wherein the gel polymer electrolyte membrane is named PNDP, the electrolyte membrane is named PND, and the commercial membrane is named GF;

[0024] Figure 5 is a graph showing the self-healing performance of the gel polymer electrolyte membrane of Example 1;

[0025] Figure 6The figures are AC impedance spectra of the gel polymer electrolyte membrane of Example 1, the electrolyte membrane of Comparative Example 1, and the commercial membrane of Comparative Example 2; wherein the gel polymer electrolyte membrane is named PNDP-1, the electrolyte membrane is named PND, and the commercial membrane is named GF;

[0026] Figure 7 The gel polymer electrolyte membrane of Example 1, the electrolyte membrane of Comparative Example 1 and the commercial membrane of Comparative Example 2 were assembled into a zinc ion battery at 1 mA / cm 2 The constant current charge and discharge curves at the current density of ; the gel polymer electrolyte separator is named PNDP, the electrolyte separator is named PND, and the commercial separator is named GF;

[0027] Figure 8 The gel polymer electrolyte membrane of Example 1 is assembled into a zinc ion battery at 1 mA / cm 2 SEM image of the zinc negative electrode surface after cycling for 200h at a current density of ;

[0028] Figure 9 The electrolyte membrane of Comparative Example 1 is assembled into a zinc ion battery at 1 mA / cm 2 SEM image of the zinc negative electrode surface after cycling for 200h at a current density of ;

[0029] Figure 10 The commercial separator of Example 2 is assembled into a zinc ion battery at 1 mA / cm 2 SEM image of the zinc negative electrode surface after cycling for 200h at a current density of . DETAILED DESCRIPTION

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0031] Unless otherwise specified, the test materials and reagents used in the following examples can be obtained from commercial sources.

[0032] If no specific techniques or conditions are specified in the examples, they can be carried out according to the techniques or conditions described in the literature in the field or according to the product instructions.

[0033] Example 1

[0034] This embodiment provides a method for preparing a gel polymer electrolyte membrane, which specifically includes the following steps:

[0035] 1. Preparation of Two-Dimensional Polymer Carboxylates

[0036] (1) Weigh 3,5-diaminobenzoic acid (250g, 1.64mol) and add it to a 2L pear-shaped flask. Then add 4L of potassium carbonate (680g, 4.92mol) aqueous solution. After stirring for 1h, slowly add acryloyl chloride (335ml, 4.10mol) in an ice-water bath. After the addition is complete, heat the mixture to room temperature and react for 4h. After the reaction is completed, adjust the mixed system with dilute hydrochloric acid (PH<3) to produce a large amount of precipitate. Let it stand for a while and filter it. Then wash the filter cake until the solution becomes colorless, put it in the refrigerator to freeze, and then place it in a freeze dryer for 2 days to remove the solvent in vacuum to obtain the target small molecule monomer DBA. Its nuclear magnetic resonance hydrogen spectrum is as follows Figure 1 shown.

[0037] (2) Weigh p-aminobenzoic acid (274g, 2mol) and place it in a 2L beaker. Add NaOH (160g, 4mol) aqueous solution. After it is completely dissolved, place it in an ice-water bath. Slowly add acryloyl chloride (244ml, 3mol). While adding, touch the wall of the cup to see the temperature change. Stop adding when the temperature rises, and continue adding after the temperature drops. After the addition is complete, remove the ice-water bath and react at room temperature for 12 hours. After the reaction is completed, slowly add 12M hydrochloric acid to acidify the reaction solution to acidity. A large amount of white solid precipitates. The filter cake obtained by filtration is washed with pure water until the solution becomes neutral. Finally, the filter cake is placed in a freeze dryer to dry to obtain a white solid, which is monomer ADA. Its nuclear magnetic resonance hydrogen spectrum is as follows Figure 2 shown.

[0038] (3) Monomer DBA (125 mg, 0.48 mmol) and monomer ADA (92 mg, 0.48 mmol) were weighed and placed in a 10 ml polymerization tube. The tube was added to 2.2 mL of deionized water and ultrasonically dispersed for 20 min to obtain a gray suspension. Subsequently, 242 μL of the organic base 1,1,3,3-tetramethylguanidine was added to the suspension. The suspension immediately became clear and transparent. The initiator potassium persulfate (7.8 mg, 0.029 mmol) was added to the suspension. The tube was frozen with liquid nitrogen to remove air, then thawed and filled with nitrogen. The operation was repeated three times. After the reaction, the mixture was placed in an oil bath and heated to 40°C. An aqueous solution of sodium thiosulfate (3.8 mg, 0.025 mmol) was prepared and injected into a 10 ml polymerization tube using a microinjector. The mixture was polymerized at 40°C for 12 hours. After the reaction, the mixture was dialyzed using a dialysis bag with a molecular weight cutoff of 8000-14000 for 48 hours, during which the water was changed 8-12 times. The polymer dialyzate was placed in a freeze dryer and freeze-dried for 72 hours to obtain a purple solid, which is the two-dimensional polymer carboxylate. The hydrogen nuclear magnetic resonance spectrum of the two-dimensional polymer carboxylate is shown in FIG. Figure 3 As shown, the double bond disappears completely, indicating that the polymerization is successful.

[0039] 2. Preparation of Gel Polymer Electrolyte Separator

[0040] (4) Weigh the cationic monomer acryloyloxyethyl trimethylammonium chloride (200 mg, 1.03 mmol), the anionic monomer sodium styrene sulfonate (200 mg, 0.96 mmol) and 2 mg of the cross-linking agent N, N-methylenebisacrylamide into a 5 ml centrifuge tube, add 1000 ml of deionized water, shake and ultrasonically mix evenly, add 5 mg of the two-dimensional polymer carboxylate prepared in step (3), shake and ultrasonically mix evenly, add 3.2 mg of the photoinitiator 2-hydroxy-2-methyl-1-phenylacetone, shake and mix evenly, pour them into a polytetrafluoroethylene plate, and polymerize under an ultraviolet lamp with a wavelength of 365 nm for 0.5 h. After the polymerization reaction is completed, remove the diaphragm from the polytetrafluoroethylene plate and dialyze in deionized water for 24 h, during which the water is changed 8-12 times to ensure that the sodium chloride is completely removed. After dialysis, soak in a 2 mol / L zinc sulfate solution for 24 h, during which the zinc sulfate solution is changed 4-5 times, and finally obtain a gel polymer electrolyte membrane.

[0041] Figure 4 is the stress-strain curve of the gel polymer electrolyte membrane of this embodiment, named PNDP. Figure 4 It can be seen that the stress is as high as 1.8MPa and the strain is close to 500%, indicating that the gel polymer electrolyte membrane has good mechanical properties.

[0042] Figure 5 is the self-healing performance diagram of the gel polymer electrolyte membrane of this embodiment, Figure 5 It can be seen that the gel polymer electrolyte membrane is cut into two sections and dyed with methyl orange and methylene blue respectively. After 2 hours, the two sections are healed together and can be folded and bent, which shows that the gel polymer electrolyte membrane has a certain self-healing ability. When the gel polymer electrolyte membrane is punctured by dendrites, it has a certain recovery ability, which can improve the battery cycle life.

[0043] Figure 6 This is the AC impedance spectrum of the gel polymer electrolyte membrane of this embodiment, named PNDP-1. Figure 6 As can be seen from the figure, the gel polymer electrolyte membrane can be tested by clamping it with a stainless steel gasket. The thickness of the membrane is 0.0566 cm and the resistance is 17.3 Ω. After calculation, the conductivity of the gel polymer electrolyte membrane is 1.7x 10 -3 S / cm.

[0044] 3. Preparation of zinc ion batteries

[0045] (5) The gel polymer electrolyte membrane obtained in step (4) is placed on a clean polytetrafluoroethylene plate and naturally air-dried until the moisture content is less than 30%. After the drying, the gel polymer electrolyte membrane is cut into 14 mm discs and assembled into a zinc ion battery for relevant electrochemical tests. The assembly order is: negative electrode shell, zinc sheet, gel polymer electrolyte membrane, zinc sheet, gasket, spring, positive electrode shell.

[0046] Figure 7 The gel polymer electrolyte separator of this embodiment is assembled into a zinc ion battery at 1mA / cm 2 The constant current charge and discharge curves tested at the current density of Figure 7 It can be seen from the graph that the voltage polarization is small and stable, and the cycle can be sustained for more than 1000 hours.

[0047] Figure 8 The gel polymer electrolyte membrane of this example is assembled into a zinc ion battery at 1mA / cm 2 The SEM image of the zinc negative electrode surface after cycling for 200h at a current density of Figure 8 It can be seen that zinc ions are evenly deposited on the surface of the electrode, indicating that the formation of long-range ordered anion and cation transport channels is conducive to the deposition of zinc ions and can effectively inhibit the formation of dendrites.

[0048] Example 2

[0049] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that: the hydrophilic monomer is the same, the cationic monomer is acrylamidomethylpropanesulfonic acid; and the anionic monomer is 2-acrylamido-2-methylpropanesulfonic acid.

[0050] Example 3

[0051] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that the hydrophilic monomer is different, the cationic monomer is vinyl pyridine, and the anionic monomer is sodium styrene sulfonate.

[0052] Example 4

[0053] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that a different cross-linking agent is used, and this embodiment uses diisocyanate.

[0054] Example 5

[0055] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that a different cross-linking agent is used, and divinylbenzene is used in this embodiment.

[0056] Example 6

[0057] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that the first initiator is different. This embodiment uses 1-hydroxycyclohexyl benzophenone.

[0058] Example 7

[0059] This embodiment provides a method for preparing a gel polymer electrolyte membrane. The difference between this embodiment and Example 1 is that the first initiator is different. This embodiment uses 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

[0060] Comparative Example 1

[0061] This comparative example provides a method for preparing an electrolyte membrane. The difference between this comparative example and Example 1 is that no two-dimensional polymer carboxylate is added. The specific preparation method is as follows:

[0062] (1) Acryloyloxyethyl trimethylammonium chloride (200 mg, 1.03 mmol), sodium styrene sulfonate (200 mg, 0.96 mmol) and 2 mg of cross-linking agent N,N-methylenebisacrylamide were weighed and placed in a 5 ml centrifuge tube. 1000 ml of deionized water was added and shaken and ultrasonically mixed. 3.2 mg of photoinitiator 2-hydroxy-2-methyl-1-phenylacetone was added and shaken and mixed. The mixture was poured into a polytetrafluoroethylene plate and polymerized under a UV lamp with a wavelength of 365 nm for 0.5 h. After the polymerization reaction was completed, the diaphragm on the polytetrafluoroethylene plate was removed and dialyzed in deionized water for 24 h. During this period, the water was changed 8-12 times to ensure that the sodium chloride was completely removed. After dialysis, the plate was soaked in a 2 mol / L zinc sulfate solution for 24 h. During this period, the zinc sulfate solution was changed four to five times to finally obtain an electrolyte membrane.

[0063] Figure 4 This is the stress-strain curve of the electrolyte membrane of this comparative example, named PND. The stress is only 0.7 MPa and the strain can only reach 200%, indicating that the mechanical properties of the electrolyte membrane are poor.

[0064] Figure 6 This is the AC impedance spectrum of the electrolyte membrane of this comparative example, named PND. Figure 6 As can be seen, the electrolyte membrane can be tested by clamping it with a stainless steel gasket. The thickness of the membrane is 0.0486 cm and the resistance is 52.8 Ω. After calculation, the conductivity of the membrane is 4.7x 10 -4 S / cm, indicating that the interfacial impedance of the electrolyte-electrode interface of the electrolyte membrane is large and the ionic conductivity is low.

[0065] (2) The electrolyte membrane obtained in step (1) is placed on a clean polytetrafluoroethylene plate and naturally air-dried until the moisture content is less than 30%. After the drying, the electrolyte membrane is cut into 14 mm discs and assembled into a zinc ion battery for relevant electrochemical tests. The assembly order is: negative electrode shell, zinc sheet, electrolyte membrane, zinc sheet, gasket, spring, positive electrode shell.

[0066] Figure 7 The electrolyte membrane of this comparative example is assembled into a zinc ion battery at 1mA / cm 2 The constant current charge and discharge curve tested at the current density of Figure 7 It can be seen that the polarization voltage is very large and the interface is extremely unstable. The voltage suddenly changes after only more than 200 hours of circulation, causing the battery to short circuit.

[0067] Figure 9 The electrolyte membrane of this comparative example is assembled into a zinc ion battery at 1mA / cm 2 The SEM image of the zinc negative electrode surface after cycling for 200h at a current density of Figure 9 It can be seen from the figure that there is uneven zinc ion deposition and zinc dendrite formation on the electrode.

[0068] Comparative Example 2

[0069] This comparative example uses a commercial separator GF, model CR2032, and assembles a zinc ion battery for relevant electrochemical tests. The assembly order is: negative electrode shell, zinc sheet, commercial separator, zinc sheet, gasket, shrapnel, and positive electrode shell.

[0070] Figure 4 This is the stress-strain curve of the commercial diaphragm of this comparative example, named GF. The stress is only 0.4 MPa and the strain can only reach 20%, indicating that the commercial diaphragm can be easily punctured by dendrites during the battery cycle.

[0071] Figure 5 This is the AC impedance spectrum of the commercial diaphragm in this comparative example, named GF. The commercial diaphragm can be tested by clamping it with a stainless steel gasket. The thickness of the commercial diaphragm is 0.0404cm, the resistance is 4.5Ω, and the conductivity is calculated to be 4.6x10 -3 S / cm.

[0072] Figure 7 The commercial separator of this comparative example is assembled into a zinc ion battery at 1mA / cm 2 The constant current charge and discharge curve tested at the current density of Figure 7 It can be seen that although the polarization voltage is very small, due to the poor mechanical properties and the lack of ion transfer channels, it is easily punctured by the produced dendrites. The glass fiber is punctured after only a hundred hours of circulation, causing a short circuit in the battery.

[0073] Figure 10 The commercial separator of this comparative example is assembled into a zinc ion battery at 1mA / cm 2 The SEM image of the zinc negative electrode surface after cycling for 200h at a current density of Figure 10 It can be seen from the figure that there is a large area of ​​uneven zinc ion deposition and dendrite growth on the electrode.

[0074] In summary, the addition of two-dimensional polymer carboxylate enhances ionic interaction, improves the mechanical properties of the gel polymer electrolyte membrane, forms long-range ordered anion and cation transfer channels, and makes the membrane have a high ionic conductivity (1.7 x 10 -3 S / cm); and the gel polymer electrolyte membrane of the present invention has certain self-healing properties. When the gel polymer electrolyte membrane is punctured by dendrites, it has a certain recovery ability, which can improve the battery cycle life; the gel polymer electrolyte membrane is assembled into a zinc ion battery, which can effectively inhibit the formation of dendrites and the occurrence of side reactions during the charge and discharge cycle, thereby improving the battery cycle life.

[0075] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A method for preparing a gel polymer electrolyte membrane, characterized in that: The method comprises the following steps: blending a two-dimensional polymer carboxylate with a hydrophilic monomer, adding a crosslinking agent and a first initiator thereto, reacting under light conditions to obtain a film; dialyzing and soaking the film to obtain a gel polymer electrolyte membrane; The preparation method of the two-dimensional polymer carboxylate is as follows: 3,5-diaminobenzoic acid and acryloyl chloride are subjected to a substitution reaction to obtain a monomer DBA; p-aminobenzoic acid and acryloyl chloride are subjected to a substitution reaction to obtain a monomer ADA; the monomers DBA and ADA are mixed, and an organic base and a second initiator are added thereto to carry out a polymerization reaction to obtain the two-dimensional polymer carboxylate.

2. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The hydrophilic monomer includes a cationic monomer and an anionic monomer, the cationic monomer includes one of acryloyloxyethyltrimethylammonium chloride, acrylamidomethylpropanesulfonic acid and vinylpyridine; the anionic monomer includes one of sodium styrenesulfonate and 2-acrylamido-2-methylpropanesulfonic acid.

3. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The crosslinking agent includes one of divinylbenzene, diisocyanate and N,N-methylenebisacrylamide.

4. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The first initiator includes one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl benzophenone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

5. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The organic base is 1,1,3,3-tetramethylguanidine; and the second initiator is potassium persulfate.

6. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The cross-linking agent accounts for 0.5% of the mass of the hydrophilic monomer.

7. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The first initiator accounts for 0.8% of the mass of the hydrophilic monomer.

8. The method for preparing a gel polymer electrolyte membrane according to claim 1, wherein: The illumination condition is under ultraviolet light with a wavelength of 365nm.

9. A gel polymer electrolyte membrane, characterized in that: The gel polymer electrolyte membrane is prepared according to the preparation method of any one of claims 1 to 8.

10. A zinc ion battery, characterized in that: The invention comprises a positive electrode, a separator and a negative electrode, wherein the separator is the gel polymer electrolyte separator according to claim 9.

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