Aqueous zinc ion battery electrolyte containing phosphate salt type anionic surfactant as well as preparation method and application of aqueous zinc ion battery electrolyte

Abstract

The invention provides an aqueous zinc ion battery electrolyte containing a phosphate salt type anionic surfactant as well as a preparation method and application of the aqueous zinc ion battery electrolyte. The electrolyte consists of soluble zinc salt, a phosphate salt type anionic surfactant additive and chromatographic water, the phosphate salt type anionic surfactant additive is adopted to modify the traditional aqueous zinc ion battery electrolyte, so that the zinc negative electrode is protected, and the cycle life of the zinc negative electrode is greatly prolonged under the condition of high utilization efficiency. The phosphate salt type anionic surfactant and water molecules in the zinc ion solvation shell layer form hydrogen bonds, so that the activity of the water molecules is inhibited, the hydrogen evolution reaction is reduced, and the utilization efficiency of the zinc negative electrode of the aqueous zinc ion battery is improved; positive ions in the phosphate salt type anionic surfactant are preferentially adsorbed on the surface of a zinc negative electrode, so that dendritic crystal growth caused by a point effect is inhibited, and the cycle life of the water-based zinc ion battery is prolonged. The problems of hydrogen evolution reaction and electrode corrosion on the zinc negative electrode side of the water-based zinc ion battery are solved, and the practical application of the water-based zinc ion battery is promoted.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of batteries, and particularly relates to a water-based zinc ion battery electrolyte containing a phosphate ester salt type anion surfactant capable of relieving dendrite growth, inhibiting hydrogen evolution reaction and improving utilization efficiency of a zinc negative electrode, and a preparation method and application thereof. BACKGROUND

[0002] With the gradual development of electronic equipment, the demand for clean energy is increasing. At present, lithium ion batteries have received more extensive attention due to the flammable and explosive problems of organic electrolyte in the face of increasing energy demand, but the safety of the organic electrolyte of the lithium ion battery cannot be fundamentally solved. Moreover, because the price of the lithium ion battery is extremely high, therefore, in the face of the current high-energy storage requirements of large capacity and low cost, we urgently need to develop safer, more affordable high-energy storage devices. Water-based zinc ion batteries are considered to be the most promising large-scale energy storage batteries due to their intrinsic safety, environmental friendliness and extremely low manufacturing cost.

[0003] Direct use of metal zinc as the negative electrode of the water-based zinc ion battery will greatly limit the use of the water-based zinc ion battery, and the severe parasitic reaction between the zinc negative electrode and the water-based electrolyte interface during the charging and discharging process will produce a large amount of reaction byproducts, induce rapid growth of dendrites, and thus pierce the separator, form internal short circuits, and affect the cycle life of the water-based zinc ion battery. In addition to the widely concerned dendrite growth problem, decomposition of solvent water molecules will cause hydrogen evolution reaction and electrode corrosion problems during the charging and discharging process, which will continuously consume the zinc negative electrode and the electrolyte, resulting in a decrease in the coulombic efficiency of the battery. Therefore, it is of great significance to develop new electrolyte additives to solve the dendrite growth and corrosion problems of the zinc metal negative electrode during the cycling process, and thus promote the practical application of the water-based zinc ion battery. SUMMARY

[0004] The application aims to provide a water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant, a preparation method and application. The electrolyte is composed of a soluble zinc salt, a phosphate salt type anionic surfactant additive and chromatographic water. The traditional water-based zinc ion battery electrolyte is modified by using the phosphate salt type anionic surfactant additive to realize the protection of the zinc negative electrode and the significant improvement of the cycle life of the zinc negative electrode under the condition of high utilization efficiency. The phosphate salt type anionic surfactant forms a hydrogen bond with water molecules in the solvation shell of zinc ions, inhibits the activity of water molecules, reduces the occurrence of hydrogen evolution reaction and improves the utilization efficiency of the zinc negative electrode of the water-based zinc ion battery. The cation in the phosphate salt type anionic surfactant is preferentially adsorbed on the surface of the zinc negative electrode, inhibits the dendrite growth caused by the tip effect and improves the cycle life of the water-based zinc ion battery. The hydrogen evolution reaction and electrode corrosion problems occurring on the zinc negative electrode side of the water-based zinc ion battery are solved, and the practical application of the water-based zinc ion battery is promoted.

[0005] The water-based zinc ion battery electrolyte containing the phosphate salt type anionic surfactant is prepared by the following steps. a. A soluble zinc salt is added to chromatographic water to prepare a water-based zinc salt electrolyte with a concentration of 1-4 mol / L; b. After the pH value of the water-based zinc salt electrolyte is stabilized at 2.5-6.2, a phosphate salt type anionic surfactant is added, and the mixture is uniformly mixed and then left to obtain a water-based zinc ion battery electrolyte containing the phosphate salt type anionic surfactant with a concentration of 1-30 mmol / L.

[0006] The preparation method of the water-based zinc ion battery electrolyte containing the phosphate salt type anionic surfactant is as follows. a. A soluble zinc salt is added to chromatographic water to prepare a water-based zinc salt electrolyte with a concentration of 1-4 mol / L; b. After the pH value of the water-based zinc salt electrolyte is stabilized at 2.5-6.2, a phosphate salt type anionic surfactant is added, and the mixture is uniformly mixed and then left to obtain a water-based zinc ion battery electrolyte containing the phosphate salt type anionic surfactant with a concentration of 1-30 mmol / L.

[0007] Use of the phosphate ester salt type anionic surfactant aqueous zinc ion battery electrolyte in the preparation of symmetric batteries, asymmetric batteries or full batteries.

[0008] The obtained phosphate ester salt type anionic surfactant aqueous zinc ion battery electrolyte is assembled with commercial zinc sheets to obtain a symmetric battery.

[0009] The obtained phosphate ester salt type anionic surfactant aqueous zinc ion battery electrolyte is assembled with commercial current collectors such as titanium foil, copper foil, nickel foil, stainless steel mesh, copper mesh, nickel mesh, foamed copper or foamed nickel to obtain an asymmetric battery.

[0010] The obtained phosphate ester salt type anionic surfactant aqueous zinc ion battery electrolyte is used as an electrolyte, commercial zinc sheets are used as negative electrodes, and commercial positive electrodes are AC / I2 or V2O5 or MnO2 or VO2 to assemble an aqueous zinc ion full battery.

[0011] The symmetric battery comprises a zinc foil working electrode, a zinc foil counter electrode and a glass fiber separator.

[0012] The asymmetric battery comprises a zinc foil working electrode and a commercial current collector counter electrode.

[0013] The commercial current collector counter electrode is a copper foil counter electrode.

[0014] The positive electrode material used in the full battery comprises iodine positive electrodes and oxide positive electrodes, specifically active carbon loaded iodine single element (AC / I2), manganese dioxide (MnO2), vanadium dioxide (VO2) and vanadium pentoxide (V2O5).

[0015] The full battery comprises a zinc foil negative electrode, an active carbon loaded iodine single element (AC / I2) positive electrode and a phosphate ester salt type anionic surfactant aqueous zinc ion battery electrolyte.

[0016] Compared with the prior art, the present application has the following advantages: The present application introduces a phosphate ester salt type anionic surfactant as an additive in the basic electrolyte, which can improve the electrolyte interface environment from multiple directions. The anion in the phosphate ester salt type anionic surfactant can change the solvation structure, reduce the activity of water and inhibit the generation of by-products; the cation in the phosphate ester salt type anionic surfactant can regulate the uniform deposition of zinc ions, relieve dendrite growth and prolong the cycle life of the battery; at the same time, the phosphate ester salt type anionic surfactant can affect the deposition behavior of zinc, so that the nucleation mode in the deposition process changes from three-dimensional progressive nucleation (3DP) to three-dimensional instantaneous nucleation (3DI), thereby improving the electrochemical performance of the aqueous zinc ion battery. At the same time, the operation process is simple and fast, the required content of the additive is less and the price is low, which is conducive to commercial use.

[0017] The application has the characteristics that: (1) The electrolyte is modified by the phosphate salt type anionic surfactant, the amount of the additive used is small, the preparation cost is low, the preparation method is simple, and large-scale production is suitable.

[0018] (2) The phosphate salt type anionic surfactant introduced in the electrolyte of the application affects the solvation structure of zinc ions through the anions of the additive, improves the utilization efficiency of the zinc negative electrode, and prolongs the cycle life of the aqueous zinc ion battery through the cations of the additive to control the deposition of zinc ions. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The time-voltage curve of the Zn||Zn symmetric battery prepared under the condition that the electrolyte containing different concentrations of phosphate salt type anionic surfactants and the electrolyte without additives have a current density of 1 mA·cm -2 , and a discharge depth of 1 mAh·cm -2 ; Figure 2 The X-ray diffraction spectrum (XRD) of the byproduct on the negative electrode surface of the Zn||Zn symmetric battery cycled to battery failure under the condition that the electrolyte containing different concentrations of phosphate salt type anionic surfactants and the electrolyte without additives have a current density of 1 mA·cm -2 , and a discharge depth of 1 mAh·cm -2 ; Figure 3 The constant current charge-discharge curve of the Zn||Zn symmetric battery containing the phosphate salt type anionic surfactant (phosphate salt type anionic surfactant additive 1 mmol / L) electrolyte and the electrolyte without additives under the condition that the current density is 2.5 mA·cm -2 , and the discharge depth is 30%; Figure 4 The zinc negative electrode scanning electron microscope image of the byproduct on the negative electrode surface of the Zn||Zn symmetric battery cycled to battery failure under the condition that the electrolyte containing different concentrations of phosphate salt type anionic surfactants and the electrolyte without additives have a current density of 1 mA·cm -2 , and a discharge depth of 1 mAh·cm -2 ; Figure 5 The Tafel curve of the three-electrode system prepared by the electrolyte containing the phosphate salt type anionic surfactant (phosphate salt type anionic surfactant additive 10 mmol / L) and the electrolyte without additives; Figure 6The cycling performance curves of Zn-AC / I2 full cells prepared with electrolytes containing phosphate ester anionic surfactants (phosphate ester anionic surfactant additive 15 mmol / L) and electrolytes without additives are shown in 1 A∙g. -1 Discharge at current density. In the figures of this application, Bare is an aqueous zinc sulfate solution (also known as an aqueous zinc salt electrolyte) with a zinc sulfate concentration of 2 mol / L; Sample is an aqueous zinc-ion battery electrolyte containing a phosphate ester anionic surfactant; Sample-1 is an aqueous zinc-ion battery electrolyte containing magnesium ascorbate phosphate with a phosphate ester anionic surfactant concentration of 1 mmol / L; Sample-5 is an aqueous zinc-ion battery electrolyte containing potassium ascorbate phosphate with a phosphate ester anionic surfactant concentration of 5 mmol / L; Sample-10 is an aqueous zinc-ion battery electrolyte containing sodium ascorbate phosphate with a phosphate ester anionic surfactant concentration of 10 mmol / L; and Sample-15 is an aqueous zinc-ion battery electrolyte containing calcium ascorbate phosphate with a phosphate ester anionic surfactant concentration of 15 mmol / L. Detailed Implementation

[0020] The present invention will now be described in more detail with reference to specific embodiments and accompanying drawings to facilitate understanding of the technical solutions of the present invention. However, this description is not intended to limit the scope of protection of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Example 1

[0021] a. Add soluble zinc salt, zinc sulfate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 3.5-4.5, add magnesium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 1 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in an ethanol solution, sonicate for 5 min, and dry it in an oven at 60℃; Preparation of electrolyte: Add 1 mmol / L of phosphate ester salt anionic surfactant additive to 2 mol / L zinc sulfate solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell.

[0022] This example demonstrates the assembly of Zn||Zn symmetric cells in electrolyte systems with different concentrations, at a current density of 1 mA∙cm⁻¹. -2 The depth of discharge is 1 mAh∙cm -2 Cycle under the given conditions, with attachment Figure 1 It can be seen that the best cycling performance is achieved when the additive concentration is 1 mmol / L; Figure 2 The image shown is an XRD pattern after cycling to battery failure in this embodiment, indicating that the addition of phosphate ester-type anionic surfactant additive can effectively suppress the formation of byproducts. Figure 3 The current density of the Zn||Zn symmetric cell is 2.5 mA∙cm⁻¹. -2 The constant current charge-discharge curves under a discharge depth of 30% show that the addition of phosphate ester salt-type anionic surfactant additives results in excellent cycle performance. Example 2

[0023] a. Add soluble zinc salt, zinc sulfate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 3.5-4.5, add potassium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 5 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; Preparation of electrolyte: Add 1 mmol / L of phosphate ester salt anionic surfactant additive to 2 mol / L zinc sulfate solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. After the battery has been cycled to the point of failure, it is disassembled, the negative electrode is cleaned, and then SEM testing is performed.

[0024] After testing in this embodiment, attached Figure 4 Image a shows a SEM image of the zinc anode surface without additives. It can be seen that obvious zinc dendrites and collapses are present on the surface. Figure 4 b is a SEM image of the zinc anode surface with added phosphate ester salt type anionic surfactant additive. It can be seen that the surface is relatively flat without large-area collapse. The electrolyte containing phosphate ester salt anionic surfactant and the electrolyte without additives obtained in this embodiment were applied to a three-electrode system with zinc foil as the working electrode, platinum sheet as the counter electrode, and Ag / AgCl electrode (0.197V vs. SHE) as the reference electrode, at 1mV s in the range of -0.6 to -1.1V. -1 Tafel plots were obtained by band scanning; The results are as follows Figure 5 As shown, the corrosion current of the electrolyte decreased from 0.0202 mA cm⁻¹ after the addition of a phosphate ester-type anionic surfactant. -2 It decreased to 0.0086 mA cm⁻¹ -2 This indicates that the addition of phosphate ester-type anionic surfactants effectively inhibited the corrosion of the zinc anode. Example 3

[0025] a. Add soluble zinc salt (zinc chloride) to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 4.5-4.8, add potassium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 5 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; To prepare the positive electrode, commercially available current collector copper foil was cut into circular pieces with a diameter of d=1cm, and half-cell tests were conducted. Preparation of electrolyte: Add 5 mmol / L of phosphate ester salt type anionic surfactant additive to 2 mol / L zinc chloride solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 4

[0026] a. Add soluble zinc salt, zinc acetate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 4 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 5.8-6.2, add magnesium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 15 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; To prepare the positive electrode, commercially available current collector titanium foil was cut into circular pieces with a diameter of d=1cm, and half-cell tests were conducted. Preparation of electrolyte: Add 15 mmol / L of phosphate ester salt type anionic surfactant additive to 4 mol / L zinc acetate solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 5

[0027] a. Add soluble zinc salt, zinc tetrafluoroborate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.5-3.5, add calcium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 1 mmol / L phosphate ester type anionic surfactant.

[0028] Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in an ethanol solution, sonicate for 5 min, and dry it in an oven at 60℃; To prepare the positive electrode, commercially available current collector nickel foil was cut into circular pieces with a diameter of d=1cm, and half-cell tests were conducted. Preparation of electrolyte: Add 1 mmol / L of phosphate ester salt anionic surfactant additive to a 2 mol / L zinc tetrafluoroborate solution and stir to mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 6

[0029] a. Add soluble zinc salt, zinc trifluoromethanesulfonyl imide, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.5-3.5, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 5 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in ethanol solution, sonicate for 5 min, and dry it in a 60℃ oven.

[0030] To prepare the positive electrode, commercially available stainless steel current collector mesh was cut into circular pieces with a diameter of d=1cm, and half-cell tests were conducted. Preparation of electrolyte: Add 5 mmol / L of phosphate salt anionic surfactant additive to a 2 mol / L zinc trifluoromethanesulfonyl imide solution and stir to mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 7

[0031] a. Add soluble zinc salts, namely zinc sulfate and zinc perchlorate, to the chromatographic water to prepare a 3 mol / L aqueous zinc salt mixed electrolyte; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.0-3.0, add magnesium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 10 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; To prepare the positive electrode, commercially available current collector foamed copper was cut into circular pieces with a diameter of d=1cm and tested for half-cell. Preparation of electrolyte: 10 mmol / L of phosphate ester type anionic surfactant additive was added to a 3 mol / L zinc sulfate and zinc perchlorate aqueous zinc salt mixed electrolyte and stirred until homogeneous to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 8

[0032] a. Add soluble zinc salt, zinc sulfate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 3.5-4.5, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 10 mmol / L phosphate ester type anionic surfactant. Preparation of the positive electrode: Ketjen black, conductive carbon black (Super P), and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 7:2:1 and methylpyrrolidone was added dropwise in a mortar. The mixture was then ground and coated onto graphite paper, and vacuum dried at 80℃ for 12 hours. The prepared substrate material was cut into circular pieces with a diameter of 1 cm and placed in a sample box. An appropriate amount of elemental iodine was added, and the sample box was sealed with a sample bag and heated at 110℃ for 12 hours. The prepared samples were tested for full-cell performance. The sample prepared at 100℃ had a capacity of 110 mAh / g, and the sample prepared at 110℃ had a capacity of 130 mAh / g. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; Preparation of electrolyte: Add 1 mmol / L of phosphate ester salt anionic surfactant additive to 2 mol / L zinc sulfate solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. In this embodiment, the assembled Zn-AC / I2 full cell is subjected to 1 A∙g -1 The cells were cycled at a current density of 88.5% and the coulombic efficiency was 88.5% after 6000 cycles, which is much higher than that of full cells with basic electrolyte. Example 9

[0033] a. Add soluble zinc salt, zinc perchlorate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 1 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 5.0-5.5, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 10 mmol / L phosphate ester type anionic surfactant. Preparation of positive electrode sheet: MnO2: conductive carbon black (Super P): polyvinylidene fluoride (PVDF) was mixed in a mass ratio of 7:2:1 and methylpyrrolidone was added dropwise in a mortar. The mixture was ground and coated onto graphite paper, and then vacuum dried at 80℃ for 12 hours. The prepared substrate material was cut into circular pieces with d=1cm. The prepared samples were then tested for full cell performance. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; Preparation of electrolyte: Add 10 mmol / L of phosphate ester salt anionic surfactant additive to 1 mol / L zinc perchlorate solution, stir and mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. In this embodiment, the assembled Zn-MnO2 full cell exhibits significantly better performance than the full cell with the basic electrolyte. Example 10

[0034] a. Add soluble zinc salt, zinc trifluoromethanesulfonate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 4 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 4.2-5.0, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 15 mmol / L phosphate ester type anionic surfactant. Preparation of positive electrode sheet: V2O5: conductive carbon black (Super P): polyvinylidene fluoride (PVDF) was mixed in a mass ratio of 7:2:1 and methylpyrrolidone was added dropwise in a mortar. The mixture was ground and coated onto graphite paper and dried under vacuum at 80℃ for 12 hours. The prepared substrate material was cut into circular sheets with d=1cm. The prepared samples were tested for full cell. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; Preparation of electrolyte: Add 15 mmol / L of phosphate ester salt anionic surfactant additive to a 4 mol / L zinc trifluoromethanesulfonate solution and stir to mix evenly to obtain a mixed electrolyte; The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. In this embodiment, the assembled Zn-V2O5 full cell exhibits significantly better performance than the full cell with the basic electrolyte. Example 11

[0035] a. Add soluble zinc salts, namely zinc sulfate and zinc perchlorate, to chromatographic water to prepare a 3 mol / L aqueous mixed zinc salt electrolyte; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.0-3.0, add potassium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 15 mmol / L phosphate ester type anionic surfactant. Preparation of positive electrode: VO2: conductive carbon black (Super P): polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 7:2:1 and methylpyrrolidone was added dropwise in a mortar. The mixture was then ground and coated onto graphite paper and vacuum dried at 80°C for 12 hours. The prepared substrate material was cut into circular pieces with a diameter of d=1cm. The prepared samples were then tested for full cell performance.

[0036] Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in ethanol solution, sonicate for 5 min, and dry it in a 60℃ oven.

[0037] Electrolyte preparation: Add 15 mmol / L of phosphate ester anionic surfactant additive to a 3 mol / L zinc sulfate and zinc perchlorate mixed solution, and stir to mix evenly to obtain a mixed electrolyte.

[0038] The battery is assembled in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell.

[0039] In this embodiment, the assembled Zn-VO2 full cell exhibits significantly better performance than the full cell with the basic electrolyte. Example 12

[0040] a. Add soluble zinc salt (zinc chloride) to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 4.5-4.8, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 15 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 13

[0041] a. Add soluble zinc salt, zinc acetate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 4 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 5.8-6.2, add sodium ascorbate phosphate, a phosphate ester type anionic surfactant. After mixing evenly, let it stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 15 mmol / L phosphate ester type anionic surfactant.

[0042] Preparation of negative electrode sheet: The zinc sheet was polished with 2000-grit sandpaper, placed in an ethanol solution, sonicated for 5 min, and then dried in an oven at 60 ℃. The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 14

[0043] a. Add soluble zinc salt, zinc trifluoromethanesulfonate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 4 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 4.2-5.0, add calcium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 20 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in an ethanol solution, sonicate for 5 min, and dry it in an oven at 60℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 15

[0044] a. Add soluble zinc salt, zinc perchlorate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 1 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 5.0-5.5, add calcium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 25 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 16

[0045] a. Add soluble zinc salt, zinc trifluoromethanesulfonyl imide, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 1 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.5-3.5, add magnesium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 30 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: The zinc sheet was polished with 2000-mesh sandpaper, placed in an ethanol solution, sonicated for 5 min, and dried in an oven at 60 ℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 17

[0046] a. Add soluble zinc salt, zinc tetrafluoroborate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 2 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.5-3.5, add potassium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 30 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in ethanol solution, sonicate for 5 min, and dry it in an oven at 60℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell. Example 18

[0047] a. Add soluble zinc salts, namely zinc sulfate and zinc perchlorate, to chromatographic water to prepare an aqueous zinc salt electrolyte with a concentration of 3 mol / L; b. After the pH of the aqueous zinc salt electrolyte stabilizes at 2.0-3.0, add magnesium ascorbate phosphate, a phosphate ester type anionic surfactant, mix well, and let stand to obtain an aqueous zinc-ion battery electrolyte with a concentration of 10 mmol / L phosphate ester type anionic surfactant. Preparation of negative electrode sheet: polish the zinc sheet with 2000-mesh sandpaper, place it in ethanol solution, sonicate for 5 min, and dry it in an oven at 60℃; The Zn||Zn symmetric cell is obtained by assembling the battery in the following steps: negative electrode shell, negative electrode sheet, glass fiber fully wetted by mixed electrolyte, positive electrode sheet, gasket, spring sheet, and positive electrode shell.

Claims

1. An aqueous zinc ion battery electrolyte containing a phosphonate salt type anionic surfactant, characterized by, The electrolyte is composed of a soluble zinc salt, a phosphate salt type anionic surfactant additive, and chromatographic water, wherein the soluble zinc salt is one or two of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc trifluoromethane sulfonate, zinc perchlorate, zinc trifluoromethanesulfonylimide, and zinc tetrafluoroborate; the phosphate salt type anionic surfactant is ascorbic acid phosphate magnesium, ascorbic acid phosphate potassium, ascorbic acid phosphate sodium, or ascorbic acid phosphate calcium, and the specific operation is performed according to the following steps: a. A soluble zinc salt is added to chromatographic water to prepare a water-based zinc salt electrolyte with a concentration of 1-4 mol / L; b. After the pH value of the water-based zinc salt electrolyte is stabilized at 2.0-6.2, a phosphate salt type anionic surfactant is added, and after uniform mixing, the mixture is left to stand, obtaining a water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant with a concentration of 1-30 mmol / L.

2. A method for producing an aqueous electrolyte for a zinc ion battery containing a phosphoric acid ester salt type anionic surfactant, characterized by, The specific operation is performed according to the following steps: a. A soluble zinc salt is added to chromatographic water to prepare a water-based zinc salt electrolyte with a concentration of 1-4 mol / L; b. After the pH value of the water-based zinc salt electrolyte is stabilized at 2.5-6.2, a phosphate salt type anionic surfactant is added, and after uniform mixing, the mixture is left to stand, obtaining a water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant with a concentration of 1-30 mmol / L.

3. Use of the phosphate salt type anionic surfactant water-based zinc ion battery electrolyte according to claim 1 or 2 in the preparation of a symmetric battery, an asymmetric battery, or a full battery.

4. Use according to claim 3, characterized in that, The obtained water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant is assembled with a commercial zinc sheet to obtain a symmetric battery.

5. Use according to claim 3, characterized in that, The obtained water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant is assembled with a commercial current collector, such as a titanium foil, a copper foil, a nickel foil, a stainless steel mesh, a copper mesh, a nickel mesh, a foamed copper, or a foamed nickel, to obtain an asymmetric battery.

6. Use according to claim 3, characterized in that, The obtained water-based zinc ion battery electrolyte containing a phosphate salt type anionic surfactant is used as an electrolyte, a commercial zinc sheet is used as a negative electrode, and a commercial positive electrode is AC / I2 or V2O5 or MnO2 or VO2 to obtain a water-based zinc ion full battery.

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