Acidic corrosion-resistant gel electrolyte, its preparation method and application

CN121618074BActive Publication Date: 2026-08-14XI'AN UNIVERSITY OF ARCHITECTURE AND TECHNOLOGY
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-12-04
Publication Date
2026-08-14

AI Technical Summary

Technical Problem

[0003]现有技术中,针对水系锌离子电池的凝胶电解质探索集中于中性体系,然而研究表明,酸性电解质在离子传输方面具有一定优势,且能够在低温条件下保持较高的离子电导率,从而展现出优异的低温电化学性能,但是目前对酸性体系的探索基本空白,原因在于:在酸性电解质条件下,金属负极及金属外壳容易发生腐蚀,导致电极结构受损和电化学性能衰减,这在一定程度上限制了金属负极低成本、易获取及高比容量优势的发挥

Benefits of technology

1、本发明提供了酸性耐腐蚀凝胶电解质,酸性耐腐蚀凝胶电解质由前驱体凝胶和电解质溶液制得,将前驱体凝胶浸泡于电解质溶液中获得酸性耐腐蚀凝胶电解质。前驱体凝胶由酸性可聚合单体、增强组分、光引发剂和交联剂经紫外光引发聚合所得,酸性可聚合单体聚合后获得聚合物基体,聚合物基体与增强组分形成三维网络结构,用于固定和储存酸性电解液,同时提高前驱体凝胶的机械强度和韧性。电解质溶液由可溶性锌盐和添加剂组成,添加剂能够在电极/电解质界面发生物理或化学作用,从而改善界面稳定性并抑制金属负极腐蚀。

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Abstract

This invention belongs to the field of aqueous zinc-ion battery technology, and particularly relates to an acidic corrosion-resistant gel electrolyte, its preparation method, and its application. The invention involves mixing an acidic polymerizable monomer, reinforcing components, a crosslinking agent, and a photoinitiator in water to obtain a precursor solution. After removing dissolved oxygen from the precursor solution, ultraviolet light is used to initiate crosslinking polymerization to form a precursor gel. The precursor gel is then soaked in an electrolyte solution to obtain an acidic corrosion-resistant gel electrolyte. The electrolyte solution is prepared by mixing soluble zinc salts and additives in water. The acidic corrosion-resistant gel electrolyte prepared using the method of this invention improves the corrosion of the metal anode by the acidic electrolyte, resulting in aqueous zinc-ion batteries with metal anodes exhibiting excellent cycle stability and extremely high ionic conductivity. Furthermore, the prepared full cells demonstrate excellent cycle stability and capacity retention under high loads.
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Description

Technical Field

[0001] This invention belongs to the field of aqueous zinc-ion battery technology, and particularly relates to acidic corrosion-resistant gel electrolytes, their preparation methods, and applications. Background Technology

[0002] With the expansion of renewable energy installations and the promotion of electric vehicles, the demand for energy storage technology is becoming increasingly prominent. Aqueous zinc-ion batteries have attracted widespread attention due to the abundance and low cost of zinc resources and their high safety. However, this system is prone to dendrite formation, hydrogen evolution, side reactions, and insufficient low-temperature performance in a liquid electrolyte environment, which seriously affects the cycle life and stability of aqueous zinc-ion batteries. To address this, researchers have proposed using a gel electrolyte to replace the liquid electrolyte in order to improve the system's cycle stability and environmental adaptability.

[0003] In the current technology, the exploration of gel electrolytes for aqueous zinc-ion batteries focuses on neutral systems. However, research shows that acidic electrolytes have certain advantages in ion transport and can maintain high ionic conductivity at low temperatures, thus exhibiting excellent low-temperature electrochemical performance. However, the exploration of acidic systems is basically blank. The reason is that under acidic electrolyte conditions, the metal anode and metal shell are prone to corrosion, which leads to damage to the electrode structure and degradation of electrochemical performance. This, to a certain extent, limits the advantages of low cost, easy availability and high specific capacity of metal anodes. Summary of the Invention

[0004] To address the shortcomings of the existing technology, this invention provides an acidic corrosion-resistant gel electrolyte, its preparation method, and its applications. In this invention, an acidic polymerizable monomer, reinforcing component, crosslinking agent, and photoinitiator are mixed in water to obtain a precursor solution. After removing dissolved oxygen from the precursor solution, ultraviolet light is used to initiate crosslinking polymerization to form a precursor gel. The precursor gel is then soaked in an electrolyte solution to obtain the acidic corrosion-resistant gel electrolyte. The electrolyte solution is prepared by mixing a soluble zinc salt and an additive, specifically an aldehyde, in water. The acidic corrosion-resistant gel electrolyte prepared using this method effectively inhibits corrosion of the metal anode, fully utilizes the performance advantages of the metal anode, and also considers low-temperature applicability. This results in aqueous zinc-ion batteries with metal anodes exhibiting excellent cycle stability and extremely high ionic conductivity. Furthermore, the prepared full cells demonstrate excellent cycle stability and capacity retention under high loads.

[0005] Based on the above technical objectives, the present invention adopts the following technical solution: This invention protects a method for preparing acidic corrosion-resistant gel electrolytes, comprising the following steps: Acidic polymerizable monomers, reinforcing components, photoinitiators, and crosslinking agents are dissolved together in deionized water to obtain a precursor solution. After removing dissolved oxygen from the precursor solution, ultraviolet light is used to initiate polymerization to form a precursor gel. The acidic polymerizable monomers have extremely low strength, and the reinforcing components can improve the strength of the precursor gel. At the same time, the effective functional groups contained therein can be coordinated and optimized with the acidic polymerizable monomers to improve electrochemical performance.

[0006] Soluble zinc salt and additives are mixed together in deionized water. The additives are used to inhibit hydrogen evolution and induce uniform zinc deposition to obtain an electrolyte solution.

[0007] The additives are one or more of the following: cinnamaldehyde, octanaldehyde, lauraldehyde, crotonaldehyde, anisaldehyde, geranialdehyde, and salicylaldehyde.

[0008] The precursor gel is immersed in an electrolyte solution and impregnated, allowing the electrolyte solution to penetrate the precursor gel, thus obtaining an acid-resistant corrosion-resistant gel electrolyte.

[0009] Preferably, the acid polymerizable monomer is selected from 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, vinyl sulfonic acid, styrene sulfonic acid, or methacrylic acid, and the pH of the acid polymerizable monomer is between 1 and 3.

[0010] Preferably, the reinforcing component is selected from gelatin, polyvinyl alcohol, cellulose, polyethylene glycol, chitosan, sodium alginate, chitin, lignin sulfonate, or carboxymethyl cellulose.

[0011] Preferably, the photoinitiator is selected from photoinitiator 2959, photoinitiator 369, photoinitiator 1173, α-ketoglutaric acid, or lithium phenyl-2,4,6-trimethylbenzoylphosphonate.

[0012] Preferably, the crosslinking agent is selected from N,N'-methylenebisacrylamide, diethylene glycol divinyl ether, or polyethylene glycol diacrylate.

[0013] Preferably, in the precursor solution, the mass ratio of acidic polymerizable monomer to reinforcing component is 2~6:1~4.

[0014] Preferably, the mass ratio of crosslinking agent to acidic polymerizable monomer is 0.5~2:100, and the mass ratio of initiator to acidic polymerizable monomer is 0.1~1:100.

[0015] Preferably, the conditions for UV-initiated polymerization are: UV irradiation at room temperature for 20 to 40 minutes. Too short a time will result in incomplete cross-linking, while too long a time will lead to aging of the precursor gel.

[0016] Preferably, the soluble zinc salt is selected from zinc sulfate, zinc chloride, zinc acetate, zinc perchlorate, or zinc trifluoromethanesulfonate.

[0017] Preferably, the concentration of soluble zinc salt in the electrolyte solution is 0.5 mol / L to 3 mol / L.

[0018] Preferably, the mass percentage of the additive in the electrolyte solution is 0.05wt% to 1.0wt%. Too much additive will hinder rapid ion transport and increase the activation energy of the reaction; too little additive will result in an insignificant optimization effect and be insufficient to protect the metal electrode from corrosion.

[0019] Preferably, the immersion treatment conditions are: soaking at room temperature for 18h to 24h.

[0020] This invention also protects an acidic corrosion-resistant gel electrolyte, which is prepared using the above-described method.

[0021] This invention also protects the application of acidic corrosion-resistant gel electrolyte in the preparation of aqueous zinc-ion batteries, which include a zinc negative electrode, an acidic corrosion-resistant gel electrolyte, and a vanadium dioxide positive electrode.

[0022] Preferably, the aqueous zinc-ion battery is a wearable flexible aqueous zinc-ion battery.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides an acid-resistant corrosion-resistant gel electrolyte, which is prepared from a precursor gel and an electrolyte solution. The precursor gel is immersed in the electrolyte solution to obtain the acid-resistant corrosion-resistant gel electrolyte. The precursor gel is obtained by ultraviolet light-initiated polymerization of an acidic polymerizable monomer, a reinforcing component, a photoinitiator, and a crosslinking agent. After polymerization, the acidic polymerizable monomer yields a polymer matrix. The polymer matrix and the reinforcing component form a three-dimensional network structure for fixing and storing the acidic electrolyte, while simultaneously improving the mechanical strength and toughness of the precursor gel. The electrolyte solution consists of a soluble zinc salt and additives. The additives can undergo physical or chemical reactions at the electrode / electrolyte interface, thereby improving interfacial stability and inhibiting metal anode corrosion.

[0024] The technical objective of this invention is to solve the problem of corrosion of metal anodes and metal casings under acidic electrolyte conditions. Based on this, corrosion resistance tests were conducted using alcohol, aldehyde, and acid. In an acidic solution without any additives, the zinc foil was completely consumed in approximately 20 minutes. While alcohol and acid could inhibit corrosion to some extent, they could only extend the corrosion time to 1-2 hours. However, after immersion in aldehyde for a week, the zinc foil still maintained its structural integrity. Research indicates that aldehydes can preferentially adsorb onto the surface of the metal electrode, preventing the metal electrode from contacting H+. + Direct contact inhibits corrosion, suppresses hydrogen evolution, and induces uniform zinc deposition.

[0025] The gel electrolyte of the present invention also has the characteristic of ultra-high ionic conductivity. The high ionic conductivity comes from the gel itself. Since the gel is prepared by using acidic polymerizable monomers as raw materials, the sulfonic acid and hydroxyl groups contained therein can promote desolvation and accelerate ion transport; while aldehydes can inhibit hydrogen evolution and induce uniform zinc deposition.

[0026] The acidic corrosion-resistant gel electrolyte of this invention maintains extremely high ionic conductivity under acidic conditions, significantly improves the cycle stability of the metal anode, and retains good electrochemical performance at low temperatures. This acidic corrosion-resistant gel electrolyte is suitable for various acidic electrolyte metal-ion battery systems, including aqueous zinc-ion batteries.

[0027] 2. The innovation of this invention compared with the prior art lies in: (1) By introducing additives into the electrolyte, the corrosion reaction between the metal anode and the acidic electrolyte is effectively suppressed in an acidic environment.

[0028] (2) This invention provides an acidic electrolyte that effectively inhibits the corrosion of metal anodes. While the metal anode is corrosion resistant, it also has the excellent properties of acidic electrolytes. The prepared acidic corrosion resistant gel electrolyte has high ionic conductivity and cycle stability, which significantly extends the battery cycle life.

[0029] (3) After solving the corrosion problem, the present invention achieves low cost, easy availability and compatibility with the excellent low-temperature performance of the metal anode with acidic electrolyte, thereby improving the reliability of aqueous zinc-ion batteries in harsh low-temperature environments.

[0030] (4) The preparation method of the present invention is highly versatile and can be applied to both acidic electrolyte systems and neutral systems, thus broadening its application scope. Attached Figure Description

[0031] Figure 1 The figure shows the pH test results after immersing the acidic corrosion-resistant gel electrolyte of Example 1 in deionized water for 24 hours.

[0032] Figure 2 This is a photograph of the acidic corrosion-resistant gel electrolyte prepared in Example 1.

[0033] Figure 3 A Zn / / gel electrolyte / / Zn symmetric cell assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1 was tested at 1 mA / cm. 2 The following is a graph showing the long-cycle stability test results.

[0034] Figure 4The graphs show a comparison of the ionic conductivity of steel / / gel electrolyte / / steel symmetric cells assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1: where graph a is the EIS curve and graph b is a comparison of the ionic conductivity calculated from graph a.

[0035] Figure 5 The graph shows the comparison of corrosion test results of zinc sheets after contact with the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1; where, graph a is for 10 min and graph b is for 200 h.

[0036] Figure 6 Tafel curves of the zinc anode in a Zn / / gel electrolyte / / Ti half-cell assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1.

[0037] Figure 7 The graph shows the long-cycle performance of the Zn / / gel electrolyte / / VO2·xH2O full cell assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1. Detailed Implementation

[0038] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0039] Considering the excellent ion transport performance of acidic electrolytes and their advantage of maintaining high ionic conductivity at low temperatures, this invention focuses on the preparation of acidic electrolytes. However, acidic electrolytes corrode metal anodes, leading to damage to the metal electrode structure and degradation of electrochemical performance. Therefore, this invention introduces additives during the preparation of acidic electrolytes to overcome the corrosive effect of acidic electrolytes on metal anodes. After screening, it was found that zinc anodes can maintain structural integrity when immersed in aldehydes for a long time. Thus, for the first time, acidic electrolytes were prepared using aldehydes as additives.

[0040] The acidity of acidic electrolytes is provided by acidic polymerizable monomers, that is, acidic gel electrolytes are directly prepared using acidic polymerizable monomers as raw materials.

[0041] Generally speaking, after introducing additives into the gel, the additive molecules adsorb onto the electrode surface, hindering ion transport. However, if... Figure 4As shown in Figure b, the research of this invention shows that introducing additives into the gel precursor can effectively improve the ionic conductivity of the acidic corrosion-resistant gel electrolyte. That is, the gel precursor and the additives can also interact to improve the ionic conductivity.

[0042] The technical solution of the present invention will be further studied using examples and comparative examples. The specific research methods and results are shown below: Example 1 The preparation method of acidic corrosion-resistant gel electrolyte includes the following steps: S1. Weigh 30g of 2-acrylamido-2-methylpropanesulfonic acid, 0.25g of N,N'-methylenebisacrylamide and 0.025g of photoinitiator 2959, and dissolve them together in 50mL of deionized water to obtain a mixture.

[0043] S2. Heat and stir the mixture continuously in a 50°C water bath, then add 20g of gelatin in batches until the gelatin is completely dissolved to obtain the precursor solution.

[0044] S3. Place the precursor liquid in a vacuum degassing device and degas for 30 minutes to remove dissolved oxygen. Then inject it into a mold and irradiate it under a 365nm ultraviolet lamp for 20 minutes to induce a photopolymerization reaction and form a gel precursor.

[0045] S4. Weigh 57.512g of zinc sulfate heptahydrate and dissolve it in 74.778g of deionized water. Then add 50μL of cinnamaldehyde and stir well to obtain a milky white electrolyte solution.

[0046] S5. Immerse the gel precursor in an electrolyte solution for 24 hours to allow it to fully absorb the electrolyte solution, thereby obtaining an acid-resistant corrosion-resistant gel electrolyte. Figure 1 The image shows the pH test results after soaking the acidic corrosion-resistant gel electrolyte in deionized water for 24 hours. The results indicate that the pH of the prepared acidic corrosion-resistant gel electrolyte remained around 2, demonstrating strong acidity. A physical image of the acidic corrosion-resistant gel electrolyte is shown below. Figure 2 As shown, it is a transparent gel.

[0047] Example 2 The preparation method of acidic corrosion-resistant gel electrolyte includes the following steps: S1. Weigh 20g of 2-acrylamido-2-methylpropanesulfonic acid, 0.2g of polyethylene glycol diacrylate and 0.02g of lithium phenyl-2,4,6-trimethylbenzoylphosphonate, and dissolve them together in 50mL of deionized water to obtain solution 1.

[0048] S2. Weigh 10g of polyvinyl alcohol and disperse it in 50mL of deionized water. Heat and stir continuously at 90℃ until the polyvinyl alcohol is completely dissolved to obtain solution 2.

[0049] S3. After mixing solution 1 and solution 2 evenly, place them in a vacuum degassing device and degas for 30 minutes to remove dissolved oxygen. Then inject them into a mold and irradiate them under a 365nm ultraviolet lamp for 30 minutes to induce a photopolymerization reaction and form a gel precursor.

[0050] S4. Weigh 6.27g of zinc acetate and dissolve it in 100g of deionized water. Then add 1mL of crotonaldehyde and stir well to obtain an electrolyte solution.

[0051] S5. Immerse the gel precursor in an electrolyte solution for 18 hours to fully absorb the electrolyte solution and obtain an acid-resistant corrosion-resistant gel electrolyte.

[0052] Example 3 The preparation method of acidic corrosion-resistant gel electrolyte includes the following steps: S1. Weigh 10g of 2-acrylamido-2-methylpropanesulfonic acid, 0.25g of N,N'-methylenebisacrylamide and 0.025g of α-ketoglutaric acid, and dissolve them together in 100mL of deionized water to obtain a mixed solution.

[0053] S2. Heat and stir the mixture continuously in a 40°C water bath, then add 5g of carboxymethyl cellulose in batches until the carboxymethyl cellulose is completely dissolved to obtain the precursor solution.

[0054] S3. Place the precursor liquid in a vacuum degassing device and degas for 30 minutes to remove dissolved oxygen. Then inject it into a mold and irradiate it under a 365nm ultraviolet lamp for 40 minutes to induce a photopolymerization reaction and form a gel precursor.

[0055] S4. Weigh 40.9g of zinc chloride and dissolve it in 100g of deionized water. Then add 50μL of anisaldehyde and stir well to obtain an electrolyte solution.

[0056] S5. Immerse the gel precursor in an electrolyte solution for 12 hours to fully absorb the electrolyte solution and obtain an acid-resistant corrosion-resistant gel electrolyte.

[0057] Comparative Example 1 The preparation method of the gel electrolyte is the same as that in Example 1, except that cinnamaldehyde is not added, and includes the following steps: Required raw materials: 2-acrylamido-2-methylpropanesulfonic acid, gelatin, zinc sulfate heptahydrate, photoinitiator 2959, N,N'-methylenebisacrylamide.

[0058] S1. Weigh 30g of 2-acrylamido-2-methylpropanesulfonic acid, 0.25g of N,N'-methylenebisacrylamide and 0.025g of photoinitiator 2959, and dissolve them together in 50mL of deionized water to obtain a mixture.

[0059] S2. Heat and stir the mixture continuously in a 50°C water bath, then add 20g of gelatin in batches until the gelatin is completely dissolved to obtain the precursor solution.

[0060] S3. Place the precursor liquid in a vacuum degassing device and degas for 30 minutes to remove dissolved oxygen. Then inject it into a mold and irradiate it under a 365nm ultraviolet lamp for 20 minutes to induce a photopolymerization reaction and form a gel precursor.

[0061] S4. Weigh 57.512g of zinc sulfate heptahydrate and dissolve it in 74.778g of deionized water to obtain an electrolyte solution.

[0062] S5. Immerse the gel precursor in an electrolyte solution for 24 hours to fully absorb the electrolyte solution and obtain the gel electrolyte.

[0063] Examples 1-3 of this invention all yielded acidic corrosion-resistant gel electrolytes with excellent performance. The following studies use the acidic corrosion-resistant gel electrolytes of Examples 1-3 and the gel electrolyte of Comparative Example 1 as examples. Specific research methods and results are shown below: Zinc-ion batteries were prepared using the acidic corrosion-resistant gel electrolytes of Examples 1-3 or the gel electrolyte of Comparative Example 1, and the specific methods are as follows: Preparation of VO2 cathode material: 0.6 g of V2O5 and 1.2 g of oxalic acid dihydrate were dissolved together in 20 mL of deionized water and heated in an 85 °C water bath for 0.5 h until the orange turbid solution turned into a dark blue transparent solution, thus obtaining a mixed solution. After cooling the mixed solution to room temperature, it was transferred to a 100 mL high-pressure reactor lined with polytetrafluoroethylene, and 50 mL of anhydrous ethanol was added. The mixture was reacted at 180 °C for 24 h to obtain a blue-black precipitate. The obtained product was washed 5 times with deionized water and then freeze-dried to obtain pure VO2·xH2O. Subsequently, VO2·xH2O, conductive carbon black, and polyvinylidene fluoride were mixed in a mass ratio of 7:2:1, and N-methylpyrrolidone was added as a dispersion medium. After thorough mixing, the mixture was coated onto a graphite paper current collector and dried in a vacuum drying oven at 60℃ for 12 hours to obtain the positive electrode sheet. The loading of VO2·xH2O on the graphite paper current collector in the positive electrode sheet was 1.0 mg / cm³. 2 ~1.5mg / cm 2 In the experimental verification of this invention, the loading amount of VO2·xH2O on the graphite paper current collector was 1.2 mg / cm³. 2 .

[0064] Assembly of button batteries: The acidic corrosion-resistant gel electrolytes of Examples 1 to 3 or the gel electrolyte of Comparative Example 1 were cut into circular pieces with a diameter of 16 mm using a cutting tool. At the same time, the negative electrode and the positive electrode were cut into circular pieces with a diameter of 14 mm. The negative electrode was selected from zinc foil or titanium foil. The batteries were assembled into symmetrical batteries, half-cells or full cells, all using a sandwich structure of positive electrode / / gel electrolyte / / negative electrode. All negative electrodes were made of zinc foil. The positive electrode side of the symmetrical battery, half-cell, and full cell used zinc foil, titanium foil, and VO2·xH2O positive electrode materials, respectively. The thickness of the prepared gel electrolyte was 2.5 mm.

[0065] Figure 3 The graphs show the long cycle life test results of zinc foil / / gel electrolyte / / zinc foil symmetric batteries assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1, respectively. The acidic corrosion-resistant gel electrolyte of Example 1 achieved an ultra-long cycle life of 2100 h, while the gel electrolyte of Comparative Example 1 only operated for 140 h. The results indicate that the prepared acidic corrosion-resistant gel electrolyte can significantly improve battery life and cycle stability.

[0066] Figure 4 The EIS test results for steel foil / / gel electrolyte / / steel foil assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1, respectively, show that the volume resistivity of the acidic corrosion-resistant gel electrolyte of Example 1 is 65.8 mS / cm, while that of the gel electrolyte of Comparative Example 1 is 56.7 mS / cm. The acidic corrosion-resistant gel electrolyte of Example 1 exhibits a smaller volume resistivity, which surpasses the ionic conductivity of the gel electrolyte of Comparative Example 1.

[0067] Figure 5 The results showed that when the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1 were contacted with zinc for 10 min, a large number of bubbles were generated on the zinc surface in contact with the gel electrolyte of Comparative Example 1, while no reaction was observed on the zinc surface in contact with the acidic corrosion-resistant gel electrolyte of Example 1. After 200 h, compared with the large-area corrosion marks on the zinc surface in contact with the gel electrolyte of Comparative Example 1, only slight corrosion marks appeared on the zinc surface in contact with the acidic corrosion-resistant gel electrolyte of Example 1.

[0068] Figure 6 The Tafel curves are for zinc foil / / gel electrolyte / / titanium foil assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1, respectively. The zinc foil / / gel electrolyte / / titanium foil assembled using the acidic corrosion-resistant gel electrolyte of Example 1 showed a more positive corrosion potential, indicating that the negative electrode of Example 1 is more corrosion-resistant.

[0069] Figure 7 The graphs show the long-cycle performance of zinc foil / / gel electrolyte / / VO2·xH2O assembled using the acidic corrosion-resistant gel electrolyte of Example 1 and the gel electrolyte of Comparative Example 1, respectively. The zinc foil / / gel electrolyte / / VO2·xH2O assembled using the gel electrolyte of Comparative Example 1 experienced rapid capacity decay and failure, while the zinc foil / / gel electrolyte / / VO2·xH2O assembled using the acidic corrosion-resistant gel electrolyte of Example 1 still showed 100% capacity retention compared to the initial capacity after 4400 cycles.

[0070] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and optimizations can be made without departing from the principle of the present invention, including improvements and optimizations of novel liquid initiators for acidic polymerizable monomers, reinforcing components, zinc salts, and additives. These improvements and optimizations should also be considered within the scope of protection of the present invention.

[0071] Those skilled in the art will readily understand that the above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an acidic corrosion-resistant gel electrolyte, characterized in that, Includes the following steps: Acidic polymerizable monomers, reinforcing components, photoinitiators and crosslinking agents are dissolved together in water to obtain a precursor solution. After removing dissolved oxygen from the precursor solution, ultraviolet light is used to initiate polymerization to form a precursor gel. The acidic polymerizable monomers are polymerized to obtain a polymer matrix. The polymer matrix and the reinforcing components form a three-dimensional network structure. A soluble zinc salt and an additive are mixed together in water to obtain an electrolyte solution; the concentration of the soluble zinc salt in the electrolyte solution is 0.5 mol / L to 3 mol / L, and the mass percentage of the additive is 0.05 wt% to 1.0 wt%. The additives are one or more of the following: cinnamaldehyde, octanaldehyde, lauraldehyde, crotonaldehyde, anisaldehyde, geranialdehyde, and salicylaldehyde. The acid polymerizable monomer is selected from 2-acrylamido-2-methylpropanesulfonic acid, acrylic acid, vinyl sulfonic acid, styrene sulfonic acid, or methacrylic acid; The reinforcing components are selected from gelatin, polyvinyl alcohol, cellulose, polyethylene glycol, chitosan, sodium alginate, chitin, lignin sulfonate, or carboxymethyl cellulose; The mass ratio of acidic polymerizable monomer to reinforcing component is 2~6:1~4; The precursor gel is immersed in an electrolyte solution and subjected to impregnation treatment to obtain an acid-resistant corrosion-resistant gel electrolyte, which is strongly acidic.

2. The method for preparing the acidic corrosion-resistant gel electrolyte according to claim 1, characterized in that, The conditions for UV-initiated polymerization are: UV irradiation at room temperature for 20 to 40 minutes.

3. The method for preparing the acidic corrosion-resistant gel electrolyte according to claim 1, characterized in that, The conditions for immersion treatment are: soaking at room temperature for 18 to 24 hours.

4. An acid-resistant, corrosion-resistant gel electrolyte, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 3.

5. The application of the acidic corrosion-resistant gel electrolyte of claim 4 in the preparation of an aqueous zinc-ion battery, characterized in that, Aqueous zinc-ion batteries consist of a zinc anode, an acidic corrosion-resistant gel electrolyte, and a vanadium dioxide cathode.

6. The application of the acidic corrosion-resistant gel electrolyte according to claim 5 in the preparation of aqueous zinc-ion batteries, characterized in that, The aqueous zinc-ion battery is a wearable, flexible aqueous zinc-ion battery.

Citation Information

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