Org / ZnSO4 electrolyte, preparation method thereof and application of Org / ZnSO4 electrolyte in secondary battery

Abstract

The invention provides an Org / ZnSO4 electrolyte, a preparation method of the Org / ZnSO4 electrolyte and application of the Org / ZnSO4 electrolyte in a secondary battery. In the Org / ZnSO4 electrolyte, a solute is Org and ZnSO4, and a solvent is deionized water and an organic solvent, or is only deionized water. Org is any one or a combination of more of aromatic organic molecules, nitrogen-containing organic molecules, fluorine-containing organic molecules or ionic compounds. The preparation method of the Org / ZnSO4 electrolyte comprises the following steps: preparing a zinc sulfate aqueous solution and an Org solution; and adding the Org solution into the zinc sulfate aqueous solution, and uniformly stirring to obtain the Org / ZnSO4 electrolyte. The Org / ZnSO4 electrolyte formula prepared by the invention is used as an aqueous zinc ion secondary battery electrolyte for the first time. Compared with the existing electrolyte, the electrolyte shows excellent corrosion resistance, rate capability and cycling stability. In addition, the Org / ZnSO4 electrolyte formula process is simple and easy to control, the controllability and efficiency of the preparation process are greatly improved, the cost is low, and industrial implementation is easy.

Description

Technical Field

[0001] The present invention belongs to the field of electrochemical power sources, and particularly relates to an Org / ZnSO 4 electrolyte, a preparation method thereof, and an application thereof in a secondary battery. Background Art

[0002] As one of the secondary batteries or rechargeable batteries for electrical energy storage and conversion, lithium-ion batteries (LIBs) have the advantages of high energy density, high cycle stability, high energy efficiency, etc., and have been successfully used as the power source for most portable electronic products and new energy vehicles, meeting the requirements of practical applications. Some characteristics of lithium-ion batteries, such as low safety, limit their application in certain fields. Specifically, the risk of safety accidents in lithium-ion batteries is relatively high, mainly due to the flammability of organic electrolytes and thermal runaway caused by the reaction between electrode materials and electrolytes. In addition, the high requirements for lithium-ion assembly technology, the need for a dry environment during the manufacturing process, the high prices of cathode transition metal materials, organic electrolytes, and lithium salts, as well as the limited lithium reserves, all lead to high manufacturing and material costs for lithium-ion batteries. In terms of safety, due to the limited ionic conductivity of organic electrolytes, a battery design with an ultra-thin electrolyte layer needs to be adopted to improve power and energy density, which is more likely to lead to high safety risks. Therefore, in order to achieve sustainable electrochemical energy storage and conversion applications, there is an urgent need to find a secondary battery energy storage system that can replace lithium-ion batteries. Compared with the high cost of lithium resources and the safety hazards of organic electrolytes in LIBs, aqueous zinc-ion batteries (AZIBs) have received extensive attention due to their safety, environmental friendliness, low cost, and simple manufacturing process. Metal zinc has the advantages of high theoretical specific capacity, up to 820 mAh / g; relatively low redox potential, as low as -0.76 V relative to the standard hydrogen electrode; high element abundance, and lower cost compared with alkali metals. In addition, the electrolyte of AZIBs is also much cheaper than the commonly used electrolyte of LIBs, and the higher safety and better ionic conductivity make AZIBs a potential electrochemical energy storage system.

[0003] Among the numerous electrolytes for AZIBs, zinc sulfate electrolyte has the advantages of high conductivity and low cost, which makes it have important application potential in the field of sustainable energy storage. In order to further improve the cycle stability of AZIBs, studies have explored the application of organic molecules and inorganic ions as additives, such as dioxane (DX) molecules and tetrabutylammonium (TBA +) Ions. For example, Patent CN118263543B discloses an aqueous zinc-ion battery electrolyte containing additives, its preparation method, and a zinc-ion battery. The electrolyte includes a zinc salt, water, and an additive; the additive is a mixture of an amino-silane coupling agent and cerium sulfate; Preparation method: Dissolve zinc sulfate in deionized water to prepare a zinc sulfate solution, then add cerium sulfate to the zinc sulfate solution, and ultrasonically disperse to prepare a homogeneous solution. Finally, add the amino-silane coupling agent to the homogeneous solution and stir well to prepare the electrolyte. An aqueous zinc-ion battery includes a positive electrode, a negative electrode, a separator, and the above-mentioned aqueous zinc-ion battery electrolyte. Applying this electrolyte to an aqueous zinc-ion battery can improve the cycle stability of the battery, prevent short circuits in the aqueous zinc-ion battery, inhibit the growth of zinc dendrites, avoid the production of by-products and hydrogen evolution corrosion, and extend the cycle life of the zinc-ion battery. Patent CN118117186A provides an electrolyte for an aqueous zinc-ion battery, its preparation method, and application. The electrolyte includes a zinc salt and vanadyl sulfate. It is prepared by the following method: Dissolve the zinc salt in water and add vanadyl sulfate, and mix and stir to obtain the electrolyte; In this invention, by adding vanadyl sulfate to the commonly used electrolytes zinc sulfate and zinc trifluoromethanesulfonate in aqueous zinc-ion batteries, the capacity and cycle stability of vanadium oxide V 2 O 5 and VO 2 as the cathode material of the aqueous zinc-ion battery are improved. The high zincophilicity of organic substances can be stably adsorbed on the surface of the zinc negative electrode, thus effectively preventing dendrites and inhibiting side reactions. Some molecules can change the solvent sheath structure of zinc ions and displace a part of the water molecules to reduce the corrosion and passivation of the zinc negative electrode surface caused by the highly active water in the desolvation process (Angew. Chem. Int. Ed. 2024, 63, e202402833; J. Am. Chem. Soc. 2024, 146, 17103). In addition, some organic / inorganic cations are stably adsorbed at the synapses on the zinc surface, playing an electrostatic shielding role in the diffusion of Zn 2+ and thus homogenizing the electric field to effectively improve the zinc deposition behavior (Nat. Commun. 2022, 13, 3252; Energy Storage Mater. 2024, 71, 103615). The introduced organic cations combine the characteristics of inorganic ions and organic substances. They can not only be effectively and stably adsorbed on the surface of the zinc anode to isolate the highly active water molecules in the desolvation process to inhibit side reactions, but also the cations on the surface can homogenize the electric field to achieve a flat and dense zinc deposition mode.

[0004] In summary, organic molecules or inorganic ions are considered an effective way to solve the interface problems of aqueous zinc-ion batteries. By introducing additives of organic molecules or inorganic ions, the stability of the interface is increased, thereby improving the electrochemical properties such as corrosion resistance, rate performance, and cycle stability of secondary batteries. Therefore, how to explore an electrolyte formulation with high stability in aqueous electrolytes has gradually become an important means to improve the interface stability of zinc negative electrode electrolytes in this field. Summary of the Invention

[0005] Based on the above-mentioned disadvantages existing in the prior art, the purpose of this application is to prepare a secondary battery with improved corrosion resistance, rate performance, and cycle stability, and to provide an Org / ZnSO 4 electrolyte and its preparation method and application in secondary batteries. This application first uses Org / ZnSO 4 as the electrolyte of an aqueous zinc-ion secondary battery. It has excellent electrochemical performance, simple preparation method, easy process control, low cost, and is easy to realize industrial mass production. It is a very promising industrial preparation method.

[0006] To achieve the above objectives, the present invention provides the following technical solutions:

[0007] One of the technical solutions of this application is to provide an Org / ZnSO 4 electrolyte. In the Org / ZnSO 4 electrolyte, the solute is Org and ZnSO 4 , and the solvent is deionized water and an organic solvent, or only deionized water; the organic solvent is any one or a combination of anhydrous ethanol, ethylene glycol, and glycerol.

[0008] Furthermore, the Org is any one or a combination of aromatic organic molecules, nitrogen-containing organic molecules, fluorine-containing organic molecules, or ionic compounds.

[0009] Further, the Org is toluene, p-xylene, 1,3,5-trimethylbenzene, benzotrichloride, benzotrifluoride, dibromotoluene, 1,2,4-trimethylbenzene, p-chlorotoluene, o-bromotoluene, 2-ethyltoluene, 3,4-dichlorotoluene, 1,2,4,5-tetramethylbenzene, 3,4-dibromotoluene, 4-ethyltoluene, 4-propyltoluene, 3,5-dibromotoluene, 2-fluorotoluene, 4-fluorotoluene, 3-bromotoluene, p-bromotoluene, o-chlorotoluene, m-chlorotoluene, p-tert-butyltoluene, 2,5-dibromoaniline, 2,4-dibromoaniline, 3,5-dibromoaniline, 2,6-dibromoaniline, 2,4,6-tribromoaniline, 3,4-dichlorobromobenzene, 1,4-dibromobenzene, 4,5-dibromo-1,2-benzenediamine, 1,4-dibromo-2,5-difluorobenzene, o-fluoroaniline, 4-fluoroaniline, m-fluorophenethylamine, 4-fluorophenyl methyl ether, m-bromofluorobenzene, 1,3-difluorobenzene, p-difluorobenzene, 3-fluorobenzamide, 1,2-difluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 2,3-difluorophenol, 4-fluorophenyl isocyanide, 2,6-difluorophenol, methylamine, ethylamine, dimethylamine, trimethylamine, aniline, benzidine, p-methylaniline, n-propylamine, isopropylamine, butylamine, acetamide, propionamide, benzamide, p-methylbenzamide, malonamide, succinamide, urea, methylformamide, dimethylformamide, diethylformamide, acetonitrile, propionitrile, butyronitrile, benzonitrile, p-methylbenzonitrile, acrylonitrile, cyanoethane, cyanobenzene, succinonitrile, malononitrile, glycine, alanine, valine, leucine, isoleucine, tryptophan, phenylalanine, tyrosine, aspartic acid, glutamic acid, asparagine, glutamine, arginine, lysine, histidine, serine, threonine, proline, cysteine, methionine, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, calcium bifluoride, zinc bifluoride, copper bifluoride, nickel bifluoride, cobalt bifluoride, iron bifluoride, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, tetrafluoroethylene, chlorotrifluoroethylene, difluorobenzene, fluorobenzene, fluorobenzene, fluorosilane, fluorophosphoric acid, fluoroalkane, fluoroolefin, fluoroalcohol, fluoroethylene, fluorochloroolefin, fluoropropene, fluorocyclohexene, fluoropropenenitrile, fluorotetrafluoroethylene, fluorocycloolefin, trifluoromethylbenzene, carbon tetrafluoride, chlorine difluoride, nitrogen tetrafluoride, sulfur hexafluoride, dimethyldifluorosilane, tetrafluoromethylbenzene, fluoroacrylic acid, 1,2-difluoroethylene, 1,At least any one of 2-difluorocyclohexene, phosphorus trifluoride, chlorofluoroethylene, fluorinated alkane, chlorofluorinated alkane, fluorinated ethylene oxide, fluorotrifluorochloroethylene, fluoro vinyl ether, sulfur difluoride, trifluoroacetic acid, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium phosphate, ammonium acetate, ammonium oxalate, ammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, 3-trifluoromethylphenyltrimethylammonium bromide, tetramethylammonium bromide or trimethylphenylammonium bromide.,

[0010] The second technical solution of the present application provides an above-mentioned Org / ZnSO 4 Preparation method of the electrolyte, the preparation method includes the following steps:

[0011] (1) Prepare an aqueous zinc sulfate solution and an Org solution respectively;

[0012] (2) Add the Org solution to the aqueous zinc sulfate solution and stir evenly to obtain the Org / ZnSO 4 electrolyte.

[0013] Furthermore, the solution preparation is carried out in a fume hood; the stirring time depends on the specific dissolution situation and is generally 20 - 40 min.

[0014] Furthermore, the molar concentration of the aqueous zinc sulfate solution is 1 - 5 mol / L, preferably 2 mol / L.

[0015] Furthermore, the molar concentration of the Org solution is 10 -5 ~10 -1 mol / L.

[0016] Furthermore, the addition volume ratio of the Org solution to the ZnSO 4 solution is 1:10 - 1:10 4 .

[0017] The third technical solution of the present application provides an application of the above-mentioned Org / ZnSO 4 electrolyte in an aqueous zinc ion secondary battery.

[0018] Furthermore, in the above application, the Org / ZnSO 4 electrolyte is used as the electrolyte of the aqueous zinc ion secondary battery to assemble a battery. The positive electrode of the battery is any one of zinc, copper, stainless steel or Mn 2+ pre-embedded vanadium pentoxide hydrate, and the negative electrode is zinc.

[0019] Compared with the prior art, the present invention has the following significant improvements:

[0020] (1) The present invention provides an Org / ZnSO with low production cost, simple and easy-to-control method, simple process, and easy industrial batch production. 4 The electrolyte and the preparation method thereof have a simple preparation process, are easy to operate, and have no by-products.

[0021] (2) Org / ZnSO 4 The electrolyte is used for the first time in aqueous zinc-ion secondary battery electrolytes. It has high specific capacity and excellent cycle stability. The performance of the aqueous zinc-ion secondary battery made by it is that the hydrogen evolution potential of the zinc / / stainless steel asymmetric battery is reduced, the corrosion potential of the zinc / / copper asymmetric battery is significantly improved, and the zinc / / zinc symmetric battery is 0.5mA / cm 2 The cycle life can reach more than 5900h at different current densities. The rate performance is excellent at different current densities. When charging and discharging at a current density of 8A / g, the discharge capacity can reach 260mAh / g, the cycle life reaches 2500 cycles, and the capacity retention rate remains above 95%. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 In Example 1, Org / ZnSO 4 Electrolyte and traditional ZnSO 4 Electrochemical performance of the electrolyte as an aqueous zinc-ion secondary battery electrolyte, (a) is the LSV test of a zinc / / stainless steel asymmetric battery, (b) is the Tafel curve of a zinc / / zinc symmetric battery, (c) is the CV curve of a zinc / / copper asymmetric battery, and (d) is the voltage-time diagram of a zinc / / zinc symmetric battery;

[0023] Figure 2 The Org / ZnSO prepared in Example 1 4 Electrolyte and traditional ZnSO 4 The full battery performance measured when the electrolyte is used as an aqueous zinc ion secondary battery electrolyte, (a) is the rate characteristics of the aqueous zinc ion secondary battery at different current densities, (b) the cycle characteristics of the aqueous zinc ion secondary battery at 8A / g;

[0024] Figure 3 For zinc anode in Org / ZnSO 4 In electrolyte at 10mA / cm 2 SEM image of the cycle at the current density of 1 h. DETAILED DESCRIPTION

[0025] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below in conjunction with specific embodiments. It should be noted that the following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0026] There are no special restrictions on the sources of all raw materials of the present invention, and those purchased on the market or prepared according to conventional methods well-known to those skilled in the art are all acceptable.

[0027] Example 1: A 3-trifluoromethylphenyltrimethylammonium bromide / ZnSO 4 electrolyte

[0028] (1) Weigh 5.75 g of zinc sulfate heptahydrate and dissolve it in 10 mL of deionized water. Stir in a fume hood for half an hour until uniform to obtain an aqueous zinc sulfate solution (Solution A, with a concentration of 2 M, the same below);

[0029] (2) Add 0.27 g of 3-trifluoromethylphenyltrimethylammonium bromide to 10 mL of deionized water and stir evenly in a fume hood to obtain a colorless and uniform Org solution (3-trifluoromethylphenyltrimethylammonium bromide solution, Solution B, with a concentration of 0.1 M, the same below);

[0030] (3) With the temperature in the fume hood at 25 °C, take the above Solution B and add it to Solution A (volume ratio A:B = 10 2 :1, the same below), mix, and continue to stir until uniform to obtain Org / ZnSO 4 electrolyte.

[0031] Example 2: A tetramethylammonium bromide / ZnSO 4 electrolyte

[0032] (1) Weigh 5.75 g of zinc sulfate heptahydrate and dissolve it in 10 mL of deionized water. Stir in a fume hood for half an hour until uniform to obtain an aqueous zinc sulfate solution (Solution A);

[0033] (2) Add 0.13 g of tetramethylammonium bromide to 10 mL of deionized water and stir evenly in a fume hood to obtain a blue and uniform Org solution (tetramethylammonium bromide solution, Solution B);

[0034] (3) With the temperature in the fume hood at 25 °C, take the above Solution B and add it to Solution A (volume ratio A:B = 10 2 :1), mix, and continue to stir until uniform to obtain tetramethylammonium bromide / ZnSO 4 electrolyte.

[0035] Example 3: A trimethylphenylammonium bromide / ZnSO 4 electrolyte solution

[0036] (1) Weigh 5.75 g of zinc sulfate heptahydrate and dissolve it in 10 mL of deionized water. Stir it in a fume hood for half an hour until it is homogeneous to obtain an aqueous zinc sulfate solution (solution A);

[0037] (2) Add 0.21 g of trimethylphenylammonium bromide to 10 mL of deionized water and stir it evenly in a fume hood to obtain a colorless and homogeneous Org solution (trimethylphenylammonium bromide solution, solution B);

[0038] (3) The temperature in the fume hood is 25 °C. Take the above solution B and add it to A (the volume ratio is A:B = 10 2 :1), mix them, and continue to stir until it is homogeneous to obtain a trimethylphenylammonium bromide / ZnSO 4 electrolyte solution.

[0039] Example 4: An aqueous zinc-ion battery made of 3-trifluoromethylphenyltrimethylammonium bromide / ZnSO 4 electrolyte solution

[0040] Take the Org / ZnSO 4 electrolyte solution (3-trifluoromethylphenyltrimethylammonium bromide / ZnSO 4 electrolyte solution) prepared in Example 1 above as the electrolyte solution of the aqueous zinc-ion battery, use a zinc sheet as the negative electrode, and use zinc, copper, and stainless steel as the positive electrodes respectively (that is, three batteries with different positive electrodes are prepared), and assemble them into a battery.

[0041] Comparative Example 1: An aqueous zinc-ion battery made of ZnSO 4 electrolyte solution

[0042] Compared with Example 4, this comparative example has no other differences except that the electrolyte solution is changed to use an aqueous ZnSO 4 solution.

[0043] Measure the performance of the aqueous zinc-ion batteries prepared in Example 4 and Comparative Example 1, including LSV curves, Tafel curves, CV curves, and voltage-time graphs. The measurement methods are as follows:

[0044] Linear sweep voltammetry (LSV) curves were tested in a zinc / / stainless steel asymmetric cell, with stainless steel as the positive electrode and zinc foil as the negative electrode. The scanning voltage range was from -0.5 to 2.5 V, and the scanning rate was 1 mV / s. Tafel curves were measured in a Zn / / Zn symmetric cell, with zinc foils as both the positive and negative electrodes. The scanning voltage range was from -0.5 to 0.5 V, and the scanning rate was 5 mV / s. Cyclic voltammetry (CV) curves were tested in a zinc / / copper asymmetric cell, with copper foil as the positive electrode and zinc foil as the negative electrode. The voltage range was from -0.5 to 0.5 V, and the scanning rate was 1 mV / s. The voltage-time plot of the zinc / / zinc symmetric cell was obtained by charging and discharging tests at 0.5 mA / cm 2 current density.

[0045] Figure 1 (a) shows the LSV test of the zinc / / stainless steel asymmetric cell, (b) shows the Tafel curve of the zinc / / zinc symmetric cell, (c) shows the CV curve of the zinc / / copper asymmetric cell, and (d) shows the voltage-time plot of the zinc / / zinc symmetric cell. The results show that: the hydrogen evolution potential of the zinc / / stainless steel asymmetric cell decreases, the corrosion potential of the zinc / / zinc symmetric cell increases significantly, the nucleation overpotential of the zinc / / copper asymmetric cell increases, and the zinc / / zinc symmetric cell can achieve a cycle life of more than 5900 h at 0.5 mA / cm 2 current density.

[0046] Example 5: An aqueous zinc-ion secondary battery made of 3-trifluoromethylphenyltrimethylammonium bromide / ZnSO 4 electrolyte

[0047] The Org / ZnSO 4 electrolyte (3-trifluoromethylphenyltrimethylammonium bromide / ZnSO 4 electrolyte) prepared in Example 1 above was used as the electrolyte of the aqueous zinc-ion secondary battery, and Mn 2+ pre-embedded hydrated vanadium pentoxide was used as the positive electrode, and a zinc sheet was used as the negative electrode to assemble the battery.

[0048] Comparative Example 2: An aqueous zinc-ion battery made of ZnSO 4 electrolyte

[0049] Compared with Example 5, this comparative example has no other differences except that the electrolyte uses ZnSO 4 aqueous solution.

[0050] The performances of the aqueous zinc-ion batteries prepared in Example 5 and Comparative Example 2 were measured, including the rate characteristics at different current densities and the cycling characteristics at 8 A / g. The measurement methods are as follows:

[0051] The negative electrode of the full cell is zinc foil, and the positive electrode is Mn 2+The pre-embedded vanadium pentoxide hydrate has its rate performance tested at a current density of 0.5 - 8 A / g. The cycle performance of the full cell is tested at a current density of 8 A / g.

[0052] Figure 2 (a) shows the rate characteristics at different current densities in the aqueous zinc-ion secondary battery, and (b) shows the cycle performance of the aqueous zinc-ion secondary battery at 8 A / g. The results show that the battery made of the Org / ZnSO 4 electrolyte provided in this application has excellent rate performance at different current densities. When charged and discharged at a current density of 8 A / g, the discharge specific capacity can reach 260 mAh / g, the cycle life reaches 2500 cycles, and the capacity retention rate remains above 95%.

[0053] Figure 3 This is the scanning electron microscope image of the zinc negative electrode after cycling for 1 h in the Org / ZnSO 4 electrolyte at a current density of 10 mA / cm 2 . The results show that the surface morphology of the electrodeposit in the Org / ZnSO 4 electrolyte is flat and dense, indicating the effective regulation of the Org on the zinc-ion deposition process and the inhibition of dendrite formation.

[0054] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and use the invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. An Org / ZnSO4 electrolyte, characterized in that: In the Org / ZnSO4 electrolyte, the solutes are Org and ZnSO4, and the solvent is deionized water and an organic solvent, or only deionized water.

2. An Org / ZnSO4 electrolyte according to claim 1, characterized in that: The organic solvent is any one or a combination of anhydrous ethanol, ethylene glycol and glycerol.

3. The Org / ZnSO4 electrolyte according to claim 1, characterized in that: The Org is any one or a combination of aromatic organic molecules, nitrogen-containing organic molecules, fluorine-containing organic molecules or ionic compounds.

4. An Org / ZnSO4 electrolyte according to claim 3, characterized in that: The Org is toluene, p-xylene, 1,3,5-trimethylbenzene, trichlorotoluene, trifluorotoluene, dibromotoluene, 1,2,4-trimethylbenzene, p-chlorotoluene, o-bromotoluene, 2-ethyltoluene, 3,4-dichlorotoluene, 1,2,4,5-tetramethylbenzene, 3,4-dibromotoluene, 4-ethyltoluene, 4-propyltoluene, 3,5-dibromotoluene, 2-fluorotoluene, 4-fluorotoluene, 3-bromotoluene, p-bromotoluene, o-chlorotoluene, m-chlorotoluene, p-tert-butyltoluene, 2,5-dibromoaniline, 2,4-dibromoaniline, 3,5-dibromoaniline, 2,6-dibromoaniline, 2,4,6-tribromoaniline, 3,4-dichlorobromoaniline Benzene, 1,4-dibromobenzene, 4,5-dibromo-1,2-phenylenediamine, 1,4-dibromo-2,5-difluorobenzene, o-fluoroaniline, 4-fluoroaniline, m-fluorophenylethylamine, 4-fluoroanisole, m-bromofluorobenzene, 1,3-difluorobenzene, p-difluorobenzene, 3-fluorobenzamide, 1,2-difluorobenzene, 1,2,3,5-tetrafluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 2,3-difluorophenol, 4-fluorophenyl isonitrile, 2,6-difluorophenol, methylamine, ethylamine, dimethylamine, trimethylamine, aniline, benzidine, p-methylaniline, n-propylamine, isopropylamine, butylamine, acetamide, propionamide, benzene Formamide, p-tolueneamide, malonamide, succinamide, urea, methylformamide, dimethylformamide, diethylformamide, acetonitrile, propionitrile, butyronitrile, benzonitrile, p-toluenenitrile, acrylonitrile, cyanoethane, cyanobenzene, succinonitrile, malononitrile, glycine, alanine, valine, leucine, isoleucine, tryptophan, phenylalanine, tyrosine, aspartic acid, glutamic acid, asparagine, glutamine, arginine, lysine, histidine, serine, threonine, proline, cysteine, methionine, ammonium fluoride, sodium fluoride, potassium fluoride, ammonium bifluoride, sodium bifluoride, potassium bifluoride, calcium bifluoride, zinc bifluoride, hydrogen fluoride Copper, nickel hydrogen fluoride, cobalt hydrogen fluoride, iron hydrogen fluoride, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, tetrafluoroethylene, chlorotrifluoroethylene, difluorobenzene, fluorobenzene, fluorinated silane, fluorinated phosphoric acid, fluorinated alkanes, fluorinated alkenes, fluorinated alcohols, fluorinated ethylene, fluorinated chloroolefins, fluorinated propylene, fluorinated cyclohexene, fluorinated acrylonitrile, fluorinated tetrafluoroethylene, fluorinated cycloolefins, trifluoromethylbenzene, carbon tetrafluoride, chlorine difluoride, nitrogen tetrafluoride, sulfur hexafluoride, difluorodimethylsilane, tetrafluoromethylbenzene, fluorinated acrylic acid, 1,2-difluoroethylene, 1,2-difluorocyclohexene, phosphorus trifluoride, fluorinated chloroolefin, fluorinated alkane, fluorinated chloroalkane, fluorinated ethylene oxide, fluorinated chlorotrifluoroolefin, fluorinated vinyl ether, sulfur difluoride, trifluoroacetic acid, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium phosphate, ammonium acetate, ammonium oxalate, ammonium hydroxide, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetraethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, 3-trifluoromethylphenyltrimethylammonium bromide, tetramethylammonium bromide or trimethylphenylammonium bromide.

5. A method for preparing the Org / ZnSO4 electrolyte according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) preparing a zinc sulfate aqueous solution and an Org solution respectively; (2) Adding the Org solution into the zinc sulfate aqueous solution and stirring evenly to obtain the Org / ZnSO4 electrolyte.

6. The method for preparing the Org / ZnSO4 electrolyte according to claim 5, characterized in that: The molar concentration of the zinc sulfate aqueous solution is 1-5 mol / L.

7. The method for preparing the Org / ZnSO4 electrolyte according to claim 5, characterized in that: The molar concentration of the Org solution is 10 -5 ~10 -1 mol / L.

8. The method for preparing the Org / ZnSO4 electrolyte according to claim 5, characterized in that: The added volume ratio of the Org solution to the ZnSO4 solution is 1:10 to 1:10 4 .

9. A use of the Org / ZnSO4 electrolyte according to any one of claims 1 to 4, characterized in that: The Org / ZnSO4 electrolyte is used to prepare an aqueous zinc ion secondary battery.

10. The use of an Org / ZnSO4 electrolyte according to claim 9, characterized in that: In the application, Org / ZnSO4 electrolyte is used as the electrolyte of aqueous zinc ion secondary battery to assemble into a battery; the positive electrode of the battery is zinc, copper, stainless steel or Mn 2+ Any of the pre-embedded hydrated vanadium pentoxides, the negative electrode being zinc.

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