A zinc battery electrolyte for constructing a zincophilic water-blocking molecular mediation layer in situ, and a preparation method and application thereof

Abstract

The application relates to the technical field of aqueous zinc ion batteries and zinc metal negative electrode interface modification, and discloses a zinc battery electrolyte for in-situ construction of a zincophilic water-blocking molecular mediated layer as well as a preparation method and application thereof. The electrolyte comprises a soluble zinc salt, an aqueous solvent and a benzene sulfonyl fluoride additive with a molecular general formula as follows: wherein R1, R2, R3, R4 and R5 are independently selected from -H, a hydroxyl group, a carboxylic acid, a fluorine group, an iodine group, a nitro group, a cyano group, an amino group, a 2-aminoethyl group, an acetylamino group, an acyl chloride group, a methyl group or a methoxy group. The benzene sulfonyl fluoride additive can be in-situ reacted at a zinc negative electrode interface to form a molecular mediated layer containing a zinc fluoride phase and a sulfonic acid root site, wherein the zinc fluoride phase promotes zinc ion conduction and uniform deposition, and the benzene sulfonic acid root site reduces the reaction activity of free water molecules through a hydrogen bond network. The electrolyte can reduce the zinc deposition overpotential, improve zinc negative electrode deposition / stripping kinetics, and help inhibit dendrite growth, hydrogen evolution and interface corrosion.

Description

Technical Field

[0001] This invention relates to the field of aqueous zinc-ion batteries and zinc metal anode interface modification technology, specifically to a zinc battery electrolyte for in-situ construction of a zinc-loving water-blocking molecule mediator layer, its preparation method, and its application. Background Technology

[0002] Lithium-ion batteries have been widely used in portable electronic devices, electric vehicles, and energy storage systems. However, traditional lithium-ion batteries typically use electrolyte systems containing flammable organic solvents, which pose safety risks under conditions of abuse, overcharging, short circuits, or thermal runaway. At the same time, the cost of raw materials related to lithium resources and some cathode materials also limits their further low-cost application in large-scale energy storage scenarios.

[0003] Compared to lithium batteries, aqueous zinc-ion batteries offer advantages such as high safety, relatively low cost, mild manufacturing conditions, and suitability for large-scale energy storage. Zinc metal anodes also possess advantages such as relatively abundant resources, good air stability, and high compatibility with aqueous electrolytes, thus they are considered an important anode system for large-scale energy storage.

[0004] However, aqueous zinc-ion batteries still face challenges during cycling, including zinc metal anode surface corrosion, hydrogen evolution reaction, and zinc dendrite growth. Non-uniform deposition on the zinc anode surface induces enhanced local electric field and continuous dendrite growth. Dendrite growth not only reduces deposition / stripping efficiency but may also lead to battery failure. Simultaneously, side reactions between active water molecules and the zinc anode can cause hydrogen evolution and interfacial corrosion, further compromising the stability of the anode surface and interface.

[0005] Existing methods for improving the stability of zinc anodes mainly include constructing an interfacial protective layer and modifying the electrolyte. While the interfacial protective layer strategy can isolate water molecules and regulate zinc ion flux to some extent, non-in-situ coating is prone to problems such as uneven coverage, local defects, and excessive coating thickness affecting zinc ion transport. The electrolyte modification strategy has the advantage of simple operation, but some systems may cause a decrease in ionic conductivity, and it is difficult to form a sufficiently stable and effective passivation layer at the zinc metal interface.

[0006] Therefore, it is still necessary to develop a simple zinc anode surface modification strategy that can simultaneously suppress zinc dendrite growth, hydrogen evolution reaction and interfacial corrosion. Summary of the Invention

[0007] The purpose of this invention is to provide a zinc battery electrolyte for in-situ construction of a zinc-loving water-blocking molecule mediator layer, its preparation method, and its application, so as to solve the problems of uneven zinc anode deposition, hydrogen evolution side reaction, and severe interface corrosion during the cycling process of aqueous zinc batteries.

[0008] To achieve the above objectives, in a first aspect, the present invention provides a zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer, comprising a soluble zinc salt, an aqueous solvent, and a benzenesulfonyl fluoride additive; the general molecular formula of the benzenesulfonyl fluoride additive is as follows: R1, R2, R3, R4, and R5 are independently selected from -H, hydroxyl, carboxylic acid, fluorine, iodo, nitro, cyano, amino, 2-aminoethyl, acetamino, acyl chloride, methyl, or methoxy.

[0009] As a further preferred embodiment of the present invention, the concentration of the soluble zinc salt in the electrolyte is 0.5~5 mol / L. - ¹; and / or, the sulfonyl fluoride additive is present in the electrolyte at a concentration of 1-10 mg / mL. - ¹.

[0010] As a further preferred embodiment of the present invention, the aqueous solvent is water, and the soluble zinc salt is selected from at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc bis(trifluoromethanesulfonate)imide, zinc perchlorate, zinc chloride, zinc nitrate, zinc acetate, zinc tetrafluoroborate, and zinc gluconate.

[0011] As a further preferred embodiment of the present invention, the sulfonyl fluoride additive is selected from benzenesulfonyl fluoride, p-methylbenzenesulfonyl fluoride, 2-nitrobenzenesulfonyl fluoride, m-nitrobenzenesulfonyl fluoride, p-nitrobenzoyl fluoride, 4-(2-aminoethyl)benzenesulfonyl fluoride, dansyl fluoride, 4-(fluorosulfonyl)benzoic acid, 3-(fluorosulfonyl)benzoic acid, 2-(fluorosulfonyl)benzoic acid, 3,5-bis(fluorosulfonyl)benzoic acid, 3,5-dicarboxybenzenesulfonyl fluoride, 2-cyanobenzenesulfonyl fluoride, 3-cyanobenzenesulfonyl fluoride, 4-cyanobenzenesulfonyl fluoride, 2-fluorobenzenesulfonyl fluoride, 3-fluorobenzenesulfonyl fluoride, 4-fluorobenzenesulfonyl fluoride, 3,5-difluorobenzenesulfonyl fluoride, 2,3-difluorobenzenesulfonyl fluoride, 2,3,4-trifluorobenzenesulfonyl fluoride, 3,4,5-trifluorobenzenesulfonyl fluoride, 2,4,5-trifluorobenzenesulfonyl fluoride. At least one of the following: sulfonyl fluoride, 2,3,5,6-tetrafluorobenzenesulfonyl fluoride, 2,3,4,5-tetrafluorobenzenesulfonyl fluoride, 2,4,5,6-tetrafluorobenzenesulfonyl fluoride, 2,3,4,5,6-pentafluorobenzenesulfonyl fluoride, 2-iodobenzenesulfonyl fluoride, 3-iodobenzenesulfonyl fluoride, 4-iodobenzenesulfonyl fluoride, 3-aminobenzenesulfonyl fluoride, 4-aminobenzenesulfonyl fluoride, 2-aminobenzene-1-sulfonyl fluoride, 3-(fluorosulfonyl)benzeneyl chloride, 4-(fluorosulfonyl)benzeneyl chloride, 4-acetaminobenzenesulfonyl fluoride, 4-hydroxybenzenesulfonyl fluoride, 3-hydroxybenzenesulfonyl fluoride, 2-hydroxybenzenesulfonyl fluoride, 3,4-dihydroxybenzenesulfonyl fluoride, 2,5-dihydroxybenzenesulfonyl fluoride, 4-methoxybenzenesulfonyl fluoride, 3-methoxybenzenesulfonyl fluoride, 2-methoxybenzenesulfonyl fluoride, and 3,4-dimethoxybenzenesulfonyl fluoride.

[0012] As a further preferred embodiment of the present invention, the zinc battery electrolyte is composed of zinc sulfate, water, and benzenesulfonyl fluoride additives; the benzenesulfonyl fluoride additives are selected from at least one of 4-(fluorosulfonyl)benzoic acid, 3-(fluorosulfonyl)benzoic acid, 2-(fluorosulfonyl)benzoic acid, 3,5-bis(fluorosulfonyl)benzoic acid, and 3,5-dicarboxybenzenesulfonyl fluoride; the content of the benzenesulfonyl fluoride additives in the electrolyte is 3~6 mg / mL. - ¹, when the additive content is 5 mg / mL - The best results are achieved under the condition that the zinc deposition overpotential is smaller.

[0013] According to a second aspect of the present invention, the present invention also provides a method for preparing the zinc battery electrolyte described in the first aspect, comprising the following steps: S1. Dissolve soluble zinc salts in an aqueous solvent to prepare a basic zinc salt electrolyte; S2. Add benzenesulfonyl fluoride additives to the basic zinc salt electrolyte and mix thoroughly to obtain a zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecular mediator layer. Preferably, the concentration of soluble zinc salt in the electrolyte is 0.5~5 mol / L. - ¹, the content of the sulfonyl fluoride additive in the electrolyte is 1~10 mg / mL. - ¹.

[0014] According to a third aspect of the present invention, the present invention also provides a zinc battery comprising the zinc battery electrolyte described in the first aspect and a zinc metal negative electrode. The zinc battery may be an aqueous zinc-ion battery, or an aqueous zinc battery such as a zinc-air battery, a zinc-halogen aqueous battery, a zinc symmetric battery, or a zinc-copper aqueous battery. In the zinc battery, a benzenesulfonyl fluoride additive forms a molecularly mediated layer containing a fluorinated zinc phase and sulfonate sites at the zinc negative electrode interface through an electrochemical reaction; wherein the fluorinated zinc phase promotes zinc ion conduction and uniform deposition, and the sulfonate sites form a hydrogen bond network with water molecules to reduce the reactivity of free water molecules.

[0015] The working principle of the electrolyte system proposed in this invention is as follows: The benzenesulfonyl fluoride group possesses high electrochemical reactivity. After gaining electrons at the zinc anode interface, the SF bond of the benzenesulfonyl fluoride group easily breaks, and the free fluoride ions combine with zinc ions to form a zinc fluoride phase. Since the zinc fluoride phase facilitates zinc ion conduction, the zinc anode interface rich in the inorganic zinc fluoride phase can stabilize zinc ion transport and promote uniform deposition. On the other hand, the sulfonate groups formed after the decomposition of the benzenesulfonyl fluoride group can form a multiple hydrogen bond network with water molecules, thereby reducing the mobility of free water molecules and weakening the corrosion of the zinc anode and hydrogen evolution side reactions by water molecules. Therefore, benzenesulfonyl fluoride additives can form a molecularly mediated layer with both zinc affinity and water-blocking characteristics in situ on the zinc anode surface.

[0016] Compared with the prior art, the present invention can achieve the following beneficial effects: First, the present invention can achieve in-situ interface control of zinc anode by directly adding a low content of benzenesulfonyl fluoride additives to aqueous zinc salt electrolyte, and the preparation method is simple. Second, the molecularly mediated layer containing zinc fluoride phase and sulfonate sites formed by the present invention can simultaneously regulate zinc ion deposition behavior and water molecule reactivity. Third, the strategy of using benzenesulfonyl fluoride compounds as additives in this invention can reduce the zinc deposition overpotential, improve zinc deposition / stripping kinetics, and help alleviate problems such as zinc dendrites, hydrogen evolution, and corrosion. Attached Figure Description

[0017] The present invention will now be described in further detail with reference to the accompanying drawings and specific embodiments.

[0018] Figure 1 The NMR spectra of the electrolytes in Example 1 and Comparative Example 1 are shown.

[0019] Figure 2 XPS F 1s spectra of the zinc anode surface and the additive 4-(fluorosulfonyl)benzoic acid molecules after one cycle of the electrolytes of Example 1 and Comparative Example 1.

[0020] Figure 3 This is a test diagram of the electrolyte wetting contact angle on the surface of the zinc negative electrode after one cycle of the electrolytes of Example 1 and Comparative Example 1.

[0021] Figure 4 The graphs show the cycle performance test results of zinc symmetric cells assembled in Example 3 and Comparative Example 1.

[0022] The objectives, features, and advantages of this invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0023] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the present invention.

[0024] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which this invention pertains. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0025] Example 1 This embodiment provides an aqueous zinc salt electrolyte for improving the electrochemical performance of zinc metal anodes, and its preparation method includes: S1. Prepare a 2 mol L solution using zinc sulfate as the solute and water as the solvent. - ¹Zinc sulfate aqueous solution is used as the basic electrolyte system for zinc batteries; S2. Dissolve 4-(fluorosulfonyl)benzoic acid, used as an additive, thoroughly and uniformly in the above-mentioned basic electrolyte system to prepare the target electrolyte, wherein the content of 4-(fluorosulfonyl)benzoic acid is 1 mg / mL. - ¹.

[0026] Example 2 The only difference from Example 1 is that the content of 4-(fluorosulfonyl)benzoic acid is 2 mg / mL. - ¹, the remaining conditions are the same as in Example 1.

[0027] Example 3 The only difference from Example 1 is that the content of 4-(fluorosulfonyl)benzoic acid is 5 mg / mL. - ¹, the remaining conditions are the same as in Example 1.

[0028] Example 4 The only difference from Example 1 is that the content of 4-(fluorosulfonyl)benzoic acid is 10 mg / mL. - ¹, the remaining conditions are the same as in Example 1.

[0029] Example 5 The only difference from Example 1 is that the additive is replaced with benzenesulfonyl fluoride, and the content of benzenesulfonyl fluoride is 1 mg / mL. - ¹, the remaining conditions are the same as in Example 1.

[0030] Example 6 The only difference from Example 1 is that the additive is replaced with 4-aminobenzenesulfonyl fluoride, and the content of 4-aminobenzenesulfonyl fluoride is 1 mg / mL. - ¹, the remaining conditions are the same as in Example 1.

[0031] Comparative Example 1 As a control experiment for Examples 1-6, a conventional aqueous zinc salt electrolyte without aromatic benzenesulfonyl fluoride additives was provided. The difference between this control and Example 1 is that the additive content was 0 mg / mL. - ¹, the composition of the remaining basic zinc salt electrolyte is the same as in Example 1.

[0032] Comparative Example 2 As a control experiment for Examples 1-6, an aqueous zinc salt electrolyte without aromatic benzenesulfonyl fluoride additives was provided. The difference between this control and Example 1 is that the additive was replaced with one containing 1 mg / mL. - ¹ Benzoic acid, and the composition of the remaining basic zinc salt electrolyte is the same as in Example 1.

[0033] The electrolytes prepared in Examples 1-6 were used as samples for in-situ construction of a zinc-loving hydrophobic molecular mediator layer on the surface of the zinc anode for battery assembly and testing. The amount of electrolyte added to each sample was 100 μL. To elucidate the electrochemical performance of the zinc anode with the in-situ constructed zinc-loving hydrophobic molecular mediator layer provided by the embodiments of the present invention, Examples 1-6 and Comparative Example 1 were used as electrolyte materials for zinc-ion batteries. For performance testing and characterization, the deposition overpotential of the zinc anode was tested by assembling a Zn|Cu battery structure, and the electrochemical cycling characteristics of the zinc anode were tested using a Zn|Zn symmetric battery. After cycling, the battery was disassembled at room temperature to clean impurities, and the surface composition and wettability of the zinc anode were tested. For the preparation of the positive electrode material for the full battery, the specific method was as follows: ZnVO powder, acetylene black, and PVDF were mixed in a ratio of 7:2:1 to prepare a slurry, which was then uniformly coated onto the surface of a titanium foil and subsequently dried in a vacuum drying oven at 80°C for 12 hours. Finally, the dried electrode sheets were cut into 12 mm diameter discs using a thin-film cutter to serve as the positive electrode material. All the batteries prepared above used GF-D glass fiber membranes as separators, and the negative electrode used unmodified zinc foil.

[0034] Tests and Results Analysis: First, the properties of the electrolytic liquid phase were compared between Example 1 and Comparative Example 1. For example... Figure 1 As shown, proton NMR spectroscopy revealed that the hydrogen atoms in Example 1 exhibited a larger chemical shift. This indicates that the sulfonate anion and carboxylic acid group corresponding to the benzenesulfonyl fluoride additive molecule, after forming a molecularly mediated layer through in-situ reaction, can act as strong hydrogen bond donors / acceptors, breaking the original hydrogen bond network of water molecules and reforming a stronger hydrogen bond network with water molecules. This result demonstrates that the addition of benzenesulfonyl fluoride additives can alter the solvation structure of the electrolyte, promote zinc ion desolvation, and inhibit hydrogen evolution side reactions, exhibiting water-blocking characteristics.

[0035] To verify the reactivity of the sulfonyl fluoride group, a Zn|Zn battery was assembled using Example 1 as the electrolyte sample, and the composition of the zinc anode surface was analyzed after only one charge-discharge cycle. Figure 2 As shown, the XPS F 1s spectrum reveals a characteristic peak representing an SF bond at 687.8 eV for the 4-(fluorosulfonyl)benzoic acid monomer. No information related to fluorine atoms was observed in Comparative Example 1, while two characteristic peaks at 687.8 eV and 684.5 eV appeared in Example 1, corresponding to the SF bond and zinc fluoride, respectively. These results indicate that the benzenesulfonyl fluoride group can undergo an in-situ reaction at the zinc anode interface, generating an interfacial component containing a zinc fluoride phase. After assembly and cycling in Examples 1 and Comparative Example 1, the electrolyte droplet contact angle was measured on the zinc anode surface. Figure 3As shown, the results indicate that the zinc anode surface corresponding to Example 1 has a smaller contact angle, indicating that the in-situ formed zinc-loving water-blocking molecule mediator layer has better interfacial affinity, which can accelerate electrolyte wetting and promote rapid ion transfer.

[0036] Furthermore, deposition efficiency was tested by assembling Zn|Cu cells. As shown in Table 1, the zinc ion deposition overpotentials of Examples 1-4 were all lower than those of Comparative Example 1, indicating that the in-situ formed zinc fluoride ion conductors facilitate the homogenization of zinc ion distribution, and the sulfonate anions obtained from the in-situ reaction can serve as zinc-loving sites to induce uniform zinc ion deposition. Example 3 exhibited the lowest deposition overpotential, indicating that, with appropriate additive ratios, the zinc-loving hydrophobic molecule-mediated layer provides superior zinc anode protection.

[0037] Furthermore, under the same addition conditions, Example 1 exhibits a lower deposition overpotential compared to Examples 5 and 6, while Comparative Example 2, using only benzoic acid, shows some improvement in deposition overpotential compared to Comparative Example 1 without additives, but the improvement is limited. In summary, this demonstrates that the carboxylic acid group in the 4-(fluorosulfonyl)benzoic acid molecule, in synergy with the sulfonate group, can further reduce the proportion of free water molecules by reconstructing multiple hydrogen bonds in the electrolyte system, significantly weakening the reactivity of water molecules. This reduces the corrosive effect of water molecules on the zinc anode and improves the efficiency of the deposition / stripping process. Simultaneously, it can reduce the accumulation of alkaline byproducts at the anode interface through acid-base interaction. Extensive experimental comparisons revealed that electrolytes using other carboxyl-substituted compounds as additives instead of the benzenesulfonyl fluoride additives of this invention exhibit significantly better electrochemical performance than those using unsubstituted benzenesulfonyl fluoride, and the additive content in the electrolyte is 4-5 mg / mL. - The effect is best when ¹.

[0038] Table 1. Comparison of deposition overpotential between the examples and comparative examples. By assembling and testing Zn|Zn symmetric cells, it can be found that, Figure 4 As shown, Example 3 exhibits a lower cycling voltage than Comparative Example 1, indicating that the zinc anode electrode reaction has superior redox kinetics. This result further demonstrates that constructing a zinc ion conductor in situ at the zinc metal interface using a highly reactive benzenesulfonyl fluoride group, and utilizing the resulting sulfonate anion as a zincophilic medium, can improve zinc ion deposition / stripping kinetics.

[0039] As shown in Table 2, when zinc anodes are combined with ZnVO cathodes to assemble zinc-ion full cells, it can be found that the average capacity of Example 3 within 500 cycles and 1000 cycles is significantly higher than that of Comparative Example 1. This indicates that the in-situ zinc-loving hydrophobic molecule mediator layer has a protective effect on the zinc anode and improves the cycle performance of zinc-ion batteries.

[0040] Table 2 Comparison of full-cell electrochemical performance between the examples and comparative examples While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and various changes or modifications can be made to these embodiments without departing from the principles and essence of the present invention. The scope of protection of the present invention is defined only by the appended claims.

Claims

1. A zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer, characterized in that, Including soluble zinc salts, aqueous solvents, and benzenesulfonyl fluoride additives; The general molecular formula of the benzenesulfonyl fluoride additive is as follows: R1, R2, R3, R4, and R5 are independently selected from -H, hydroxyl, carboxylic acid, fluorine, iodo, nitro, cyano, amino, 2-aminoethyl, acetamino, acyl chloride, methyl, or methoxy.

2. The zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer according to claim 1, characterized in that, The concentration of the soluble zinc salt in the electrolyte is 0.5~5 mol / L. - ¹; and / or, the sulfonyl fluoride additive is present in the electrolyte at a concentration of 1-10 mg / mL. - ¹.

3. The method for preparing zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer according to claim 1, characterized in that, The aqueous solvent is water, and the soluble zinc salt is selected from at least one of zinc sulfate, zinc trifluoromethanesulfonate, zinc bis(trifluoromethanesulfonate)imide, zinc perchlorate, zinc chloride, zinc nitrate, zinc acetate, zinc tetrafluoroborate, and zinc gluconate.

4. The zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer according to claim 1, characterized in that, The sulfonyl fluoride additives are selected from benzenesulfonyl fluoride, p-methylbenzenesulfonyl fluoride, 2-nitrobenzenesulfonyl fluoride, m-nitrobenzenesulfonyl fluoride, p-nitrobenzoyl fluoride, 4-(2-aminoethyl)benzenesulfonyl fluoride, 4-(fluorosulfonyl)benzoic acid, 3-(fluorosulfonyl)benzoic acid, 2-(fluorosulfonyl)benzoic acid, 3,5-bis(fluorosulfonyl)benzoic acid, 3,5-dicarboxybenzenesulfonyl fluoride, 2-cyanobenzenesulfonyl fluoride, 3-cyanobenzenesulfonyl fluoride, 4-cyanobenzenesulfonyl fluoride, 2-fluorobenzenesulfonyl fluoride, 3-fluorobenzenesulfonyl fluoride, 4-fluorobenzenesulfonyl fluoride, 3-fluorobenzenesulfonyl fluoride, 4-fluorobenzenesulfonyl fluoride, 3,5-difluorobenzenesulfonyl fluoride, 2,3-difluorobenzenesulfonyl fluoride, 2,3,4-trifluorobenzenesulfonyl fluoride, 3,4,5-trifluorobenzenesulfonyl fluoride, 2,4,5-trifluorobenzenesulfonyl fluoride, 2,3,5- At least one of the following: 6-tetrafluorobenzenesulfonyl fluoride, 2,3,4,5-tetrafluorobenzenesulfonyl fluoride, 2,4,5,6-tetrafluorobenzenesulfonyl fluoride, 2,3,4,5,6-pentafluorobenzenesulfonyl fluoride, 2-iodobenzenesulfonyl fluoride, 3-iodobenzenesulfonyl fluoride, 4-iodobenzenesulfonyl fluoride, 3-aminobenzenesulfonyl fluoride, 4-aminobenzenesulfonyl fluoride, 2-aminobenzene-1-sulfonyl fluoride, 3-(fluorosulfonyl)benzeneyl chloride, 4-(fluorosulfonyl)benzeneyl chloride, 4-acetaminobenzenesulfonyl fluoride, 4-hydroxybenzenesulfonyl fluoride, 3-hydroxybenzenesulfonyl fluoride, 2-hydroxybenzenesulfonyl fluoride, 3,4-dihydroxybenzenesulfonyl fluoride, 2,5-dihydroxybenzenesulfonyl fluoride, 4-methoxybenzenesulfonyl fluoride, 3-methoxybenzenesulfonyl fluoride, 2-methoxybenzenesulfonyl fluoride, and 3,4-dimethoxybenzenesulfonyl fluoride.

5. The zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecule-mediated layer according to claim 1, characterized in that, The zinc battery electrolyte is composed of zinc sulfate, water, and benzenesulfonyl fluoride additives; the benzenesulfonyl fluoride additives are selected from at least one of 4-(fluorosulfonyl)benzoic acid, 3-(fluorosulfonyl)benzoic acid, 2-(fluorosulfonyl)benzoic acid, 3,5-bis(fluorosulfonyl)benzoic acid, and 3,5-dicarboxybenzenesulfonyl fluoride; the content of the benzenesulfonyl fluoride additives in the electrolyte is 3~6 mg / mL. - ¹.

6. A method for preparing a zinc battery electrolyte for in-situ construction of a zinc-loving, water-blocking molecular mediator layer as described in any one of claims 1-5, characterized in that, Includes the following steps: S1. Dissolve soluble zinc salts in an aqueous solvent to prepare a basic zinc salt electrolyte; S2. Add benzenesulfonyl fluoride additives to the basic zinc salt electrolyte and mix thoroughly to obtain a zinc battery electrolyte for in-situ construction of a zinc-loving water-blocking molecule mediator layer.

7. The application of the zinc battery electrolyte according to any one of claims 1 to 5 in zinc batteries.

8. A zinc battery, characterized in that, It includes the zinc battery electrolyte and zinc metal negative electrode as described in any one of claims 1 to 5.

9. The zinc battery according to claim 8, characterized in that, The benzenesulfonyl fluoride additive forms a molecularly mediated layer containing a zinc fluoride phase and sulfonate sites at the zinc anode interface through an electrochemical reaction; wherein, the zinc fluoride phase is used to promote zinc ion conduction and uniform deposition, and the sulfonate sites are used to form a hydrogen bond network with water molecules to reduce the reactivity of free water molecules.

10. The zinc battery according to claim 8, characterized in that, The zinc battery is an aqueous zinc-ion battery, a zinc-air battery, a zinc-halogen aqueous battery, a zinc symmetric battery, or a zinc-copper aqueous battery.

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