All-weather zinc-based battery hydration deep eutectic electrolyte and application thereof

Abstract

The application discloses a low-cost hydrated deep eutectic electrolyte and application thereof in zinc ion batteries in all-weather wide temperature range. The hydrated deep eutectic electrolyte comprises a hydrated zinc salt, a hydrogen bond coordination small molecule containing a specific functional group and an additional solvent, wherein the hydrated zinc salt is one of Zn(ClO4)2.6H2O, Zn(BF4)2.6H2O and ZnSO4.7H2O; the coordination hydrogen bond small molecule is at least one of acetyl propyl alcohol, acetyl propyl acetone and acetyl propyl acid; and the solvent is water. The application enriches the types of zinc ion solvation structures and regulates the hydrogen bond network by optimizing the complex interaction of each component in the hydrated deep eutectic electrolyte, and regulates the proportion of active water, so that the stability of the electrolyte system state in the all-weather range of-20 to 50 DEG C is realized, and the application is applied to energy supply in a wide temperature environment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of battery electrolyte, and particularly relates to a hydrated deep eutectic electrolyte and application thereof. BACKGROUND

[0002] Lithium ion batteries have the advantages of high energy density, long cycle life and low self-discharge rate, and are the mainstream secondary batteries in today's society, playing an important role in the fields of electronic devices, energy, etc. However, the lithium ion batteries have the shortcomings of high manufacturing cost and low safety, while the emerging aqueous zinc ion battery has the characteristics of high energy density, low cost and safety and environmental protection, and has attracted much attention from researchers.

[0003] However, the aqueous zinc ion battery electrolyte contains a large amount of water, which leads to a series of problems, such as positive electrode dissolution, negative electrode corrosion, passivation and hydrogen evolution reaction, etc. The electrolyte, as the 'blood' of the battery, plays an irreplaceable role in the efficient cycle of the battery. In order to solve the above problems, the reported works mainly improve the above problems by designing high-concentration electrolyte, ionic liquid, hydrogel and other strategies. However, these methods are toxic and high in cost, which completely deviates from the advantages of safety and low cost of the aqueous zinc battery.

[0004] Deep eutectic solvents (DESs), as a eutectic system solvent composed of hydrogen bond donors (HBD) and hydrogen bond acceptors (HBA), have attracted extensive attention in recent years due to their environmental friendliness and sustainability of biological sources. Therefore, in order to promote the application of aqueous zinc ion battery in large-scale energy storage field, it is particularly important to further develop a safe, environmentally friendly and wide temperature range zinc-based eutectic electrolyte. SUMMARY

[0005] In order to solve the bottleneck problems of the aqueous zinc battery in low temperature or high temperature environment, the primary purpose of the present application is to provide a low-cost, simple ratio and full-weather wide temperature range hydrated deep eutectic electrolyte which can work stably from low temperature to high temperature.

[0006] Another purpose of the present application is to provide the application of the above-mentioned hydrated deep eutectic electrolyte. The hydrated deep eutectic electrolyte can be used for the preparation of aqueous zinc battery and effectively applied to various harsh environment scenes.

[0007] Another purpose of the present application is to provide a full-weather aqueous zinc-based battery. The full-weather aqueous zinc-based battery can stably and reversibly operate in the temperature range of-2050℃.

[0008] The purpose of the present application is realized by the following scheme:

[0009] A full-weather zinc-based battery hydrated deep eutectic electrolyte, characterized in that the electrolyte is composed of a zinc salt, a hydrogen bond ligand and an additional water solvent.

[0010] Further, the volume ratio of the water solvent and the hydrogen bond ligand is 1:1-5, and the concentration of the zinc salt aqueous solution in the electrolyte is maintained at 2 mol·L-1.

[0011] Further, the zinc salt includes at least one of Zn(ClO4)2·6H2O, Zn(BF4)2·6H2O and ZnSO4·7H2O.

[0012] Further, the hydrogen bond ligand includes at least one of acetyl propyl alcohol, acetyl propyl ketone and acetyl propyl acid.

[0013] Secondly, the application also includes the preparation of the all-weather zinc-based battery hydration deep eutectic electrolyte for the all-weather zinc-based battery.

[0014] In addition, the application also includes an all-weather aqueous zinc-based battery, characterized in that it comprises a positive electrode, a negative electrode and an all-weather zinc-based battery hydration deep eutectic electrolyte, and the preparation method of the positive electrode is to load at least one of a conductive polymer and a vanadium-based compound on a substrate.

[0015] Further, the conductive polymer is at least one of polyaniline and polypyrrole; the vanadium-based compound is at least one of vanadium dioxide, divanadium pentoxide, sodium vanadate, zinc metavanadate, sodium vanadate phosphate and sodium vanadate metaphosphate; the substrate is commercial carbon paper and acid-etched and roughened titanium foil; the loading amount of at least one of the conductive polymer and the vanadium-based compound on the substrate is 2-20 mg·cm -2 , the electrode thickness is 0.15-1.5 mm, and the tap density is 0.6-3.5 g / cm 3 .

[0016] Further, the loading method includes in-situ polymerization, blade coating film formation or hydrothermal synthesis; the negative electrode is a high-purity zinc metal foil with a thickness of 10-100 μm, or a zinc thin film obtained by anodic deposition or brush coating of zinc slurry on a titanium foil, a stainless steel foil or carbon paper, with a thickness controlled at 5-30 μm.

[0017] Finally, the application also includes a preparation method of the all-weather aqueous zinc-based battery, characterized in that it comprises the following steps: assembling the positive electrode, the hydration deep eutectic electrolyte and the negative electrode into an aqueous zinc ion battery with different device structures.

[0018] Further, the method is specifically to use glass fiber as a separator, and if a standard button shell is used to package into a button cell at a pressure of 70-90 MPa, the added amount of the hydration deep eutectic electrolyte is 50-100 μL.

[0019] The mechanism of the application is that the hydrogen bond coordination small molecule regulates the behavior of complex water molecules, and then participates in the Zn 2+solubility behavior of Zn 2+ Furthermore, the hydrogen bond coordination of the polar oxygen-rich functional groups of the small molecules with the anions in the hydrated zinc salt or water molecules forms a strong hydrogen bond interaction, which regulates the behavior of active free water molecules to inhibit the occurrence of hydrogen evolution side reactions, and at the same time, with a large binding energy, it is adsorbed on the surface of the zinc negative electrode, greatly reducing the occurrence of corrosion side reactions. It is worth noting that as the main component of the electrolyte, the hydrogen bond coordination of the small molecules controls the content of active water molecules from the source, greatly reduces the mutual hydrogen bond interaction between active water molecules, and effectively inhibits the formation of tetrahedral water molecules required for freezing. Among them, because the organic coordination small molecules are widely involved in the structure formation of the eutectic electrolyte system at room temperature, the solvation structure type and distribution uniformity of zinc ions are significantly increased, the structure mutation of the electrolyte under high temperature environment is effectively stabilized, and the evaporation of active water molecules is accelerated. Finally, by further regulating the content of the additional water molecules introduced, the ion conductivity and other transport kinetic properties of the hydrated deep eutectic electrolyte system can be optimized, solving the bottleneck of insufficient ion transport capacity at low temperature and the poor stability under high temperature environment.

[0020] Compared with the prior art, the present application has the following advantages and beneficial effects:

[0021] The all-weather zinc-based hydrated deep eutectic electrolyte provided by the present application is formed by mixing zinc salt and hydrogen bond ligand to form a eutectic solvent, which is in a liquid state at room temperature. Through hydrogen bond interaction, the solubility of zinc salt and hydrogen bond ligand is improved, thereby improving the conductivity of the battery and the stability of the electrolyte. Importantly, the electrolyte of the present application exhibits high charge and discharge capacity and excellent cycle stability under all-weather conditions (-20℃ to 50℃), effectively expanding the working temperature range of the aqueous zinc ion battery, solving the problems of zinc negative electrode side reactions and dendrite growth at high and low temperatures, greatly prolonging the service life of the aqueous zinc ion battery, and having important significance in the field of energy storage. Moreover, the preparation method of the all-weather zinc-based hydrated deep eutectic electrolyte provided by the present application is simple, fast, low in cost, safe, green and pollution-free, and is suitable for large-scale popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 Long cycle diagram of the Zn-Zn battery assembled by the electrolyte in Example 1 and Comparative Example 1 at 25℃;

[0023] Figure 2 Charge and discharge cycle performance diagram of the Zn-Zn battery assembled by the electrolyte in Example 2 and Comparative Example 2 at 50℃;

[0024] Figure 3 Cycle performance diagram of the Zn-Zn battery assembled by the electrolyte in Example 3 and Comparative Example 3 at -20℃;

[0025] Figure 4 XRD test pattern of Zn-Zn battery assembled with electrolyte of Example 4 and Comparative Example 4 at 25℃;

[0026] Figure 5 SEM test pattern of Zn-Zn battery of Example 5 and Comparative Example 5 at 25℃;

[0027] Figure 6 Long cycle performance pattern of Zn||VOX battery of Example 6 and Comparative Example 6 at 25℃. DETAILED DESCRIPTION

[0028] In order to make the above objectives, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the accompanying drawings, but the present application can be implemented in many other ways different from those described herein, and therefore the present application is not limited by the specific implementations disclosed below.

[0029] Example 1

[0030] A full-weather zinc-based battery hydration deep eutectic electrolyte, levulinic acid and deionized water are mixed in a volume ratio of 1:1 at room temperature, and then zinc sulfate is added as a solute, and the concentration is controlled to be 2mol / L, and stirred at room temperature for 60min, to obtain a clear and transparent electrolyte, named DES50. The effect of levulinic acid on inducing uniform deposition of zinc ions is verified by using the above-mentioned hydration deep eutectic electrolyte.

[0031] Zinc foil is used as the positive and negative electrode, and glass fiber is used as the separator, and 120μL of the above-mentioned electrolyte is taken to assemble a CR2032 type button symmetric battery, and the cyclic charge-discharge test is carried out on the new Wei battery test system. The test temperature is 25℃, the current density is 5mA·cm -2 , and the surface capacity is 1mAh·cm -2 .

[0032] Comparative Example 1

[0033] At room temperature, 14.378g of zinc sulfate heptahydrate is added to 25ml of deionized water and ultrasonically dispersed for 20min to prepare a 25ml electrolyte containing 2mol / L zinc sulfate, named DES0.

[0034] Zinc foil is used as the positive and negative electrode, and glass fiber is used as the separator, and 120μL of the above-mentioned electrolyte is taken to assemble a CR2032 type button symmetric battery, and the cyclic charge-discharge test is carried out on the new Wei battery test system. The test temperature is 25℃, the current density is 5mA·cm -2 , and the surface capacity is 1mAh·cm -2 .

[0035] The test results are as follows Figure 1As shown, the symmetrical battery assembled using Comparative Example 1 experienced a reduced cycle life due to side reactions such as zinc dendrite formation and hydrogen evolution corrosion during cycling. In contrast, Example 1, assembled with the zinc-based hydrated deep eutectic electrolyte prepared in this invention, significantly extended the battery's cycle life; specifically, DES50 could cycle for approximately 1800 hours. Simultaneously, the addition of a certain volume fraction of levulinic acid reduced the polarization voltage of the hydrated deep eutectic electrolyte.

[0036] Example 2

[0037] A hydrated deep eutectic electrolyte for all-weather zinc-based batteries is prepared by mixing levulinic acid and deionized water at a volume ratio of 1:1 at room temperature as a solvent, followed by the addition of zinc sulfate to a concentration controlled at 2 mol / L. The mixture is then stirred at room temperature for 60 min to obtain a clear and transparent electrolyte, named DES50. The effect of levulinic acid on inducing uniform zinc ion deposition is verified using this hydrated deep eutectic electrolyte.

[0038] Using zinc foil as the positive and negative electrodes and glass fiber as the separator, 120 μL of the above electrolyte was used to assemble a CR2032 coin cell. Cyclic charge-discharge tests were then conducted on the Xinwei Battery Testing System. The test temperature was 50℃, and the current density was 0.25 mA·cm². -2 The surface capacity is 0.25 mAh·cm³. -2 .

[0039] Comparative Example 2

[0040] At room temperature, 14.378 g of zinc sulfate heptahydrate was added to 25 ml of deionized water and sonicated for 20 min to disperse it completely, thus preparing an electrolyte containing 2 mol / L zinc sulfate in 25 ml, which was named DES0.

[0041] Using zinc foil as the positive and negative electrodes and glass fiber as the separator, 120 μL of the above electrolyte was used to assemble a CR2032 coin cell. Cyclic charge-discharge tests were then conducted on the Xinwei Battery Testing System. The test temperature was 50℃, and the current density was 0.25 mA·cm². -2 The surface capacity is 0.25 mAh·cm³. -2 .

[0042] Test results are as follows Figure 2 As shown, the symmetrical battery assembled using Comparative Example 2 exhibits accelerated side reactions such as zinc dendrite formation and hydrogen evolution corrosion during cycling at 50°C, resulting in a cycle life of only about 50 hours, significantly shortening the battery's cycle life. In contrast, the Zn-Zn battery assembled using the zinc-based eutectic electrolyte in Example 2 can cycle for about 200 hours, demonstrating the good applicability of the zinc-based hydrated deep eutectic electrolyte prepared in this invention under high-temperature conditions.

[0043] Example 3

[0044] A full-weather zinc-based battery hydration deep eutectic electrolyte, levulinic acid and deionized water are mixed in a volume ratio of 1:1 at room temperature, and then zinc sulfate is added as a solute, and the concentration is controlled at 2 mol / L, and stirred at room temperature for 60 min, to obtain a clear and transparent electrolyte, named DES50. The effect of levulinic acid on inducing uniform deposition of zinc ions is verified by using the above-mentioned hydration deep eutectic electrolyte.

[0045] Zinc foil is used as the positive and negative electrode, and glass fiber is used as the separator. 120 μL of the above-mentioned electrolyte is taken to assemble a CR2032 type button symmetric battery, and the cyclic charge-discharge test is carried out on the new Wei battery test system. The test temperature is 50℃, the current density is 0.25 mA·cm -2 , and the surface capacity is 0.25 mAh·cm -2 .

[0046] Comparative Example 3

[0047] At room temperature, 14.378 g of zinc sulfate heptahydrate is added to 25 ml of deionized water and ultrasonically dispersed for 20 min to prepare a 25 ml electrolyte containing 2 mol / L zinc sulfate, named DES0.

[0048] Zinc foil is used as the positive and negative electrode, and glass fiber is used as the separator. 120 μL of the above-mentioned electrolyte is taken to assemble a CR2032 type button symmetric battery, and the cyclic charge-discharge test is carried out on the new Wei battery test system. The test temperature is -20℃, the current density is 0.25 mA·cm -2 , and the surface capacity is 0.25 mAh·cm -2 .

[0049] The test results are shown in Figure 2 , using the symmetric battery assembled in Comparative Example 2, under the condition of -20℃, due to the decrease in temperature, the symmetric battery of Comparative Example 3, the ion transport process is hindered, the impedance increases, and can only be cycled for about 120 hours. In contrast, the Zn-Zn battery assembled by the zinc-based eutectic electrolyte selected in Example 3 can be stably cycled for about 720 hours, showing good electrochemical performance, which shows that the zinc-based hydration deep eutectic electrolyte prepared by the application has good applicability under low temperature conditions.

[0050] Example 4

[0051] A kind of all-weather zinc-based battery hydration deep eutectic electrolyte, acetylpicolinic acid is mixed with deionized water according to the volume ratio of 1:1, and stirred at room temperature as solvent, then add solute zinc sulfate, make its concentration control 2mol / L, stir 60min at room temperature, obtain clear and transparent electrolyte, named as DES50.The effect of acetylpicolinic acid on inhibiting the occurrence of side reaction is verified using the above zinc-based hydration deep eutectic electrolyte.

[0052] Using zinc foil as positive and negative electrode, glass fiber as diaphragm, 120 μL of the above electrolyte is taken to assemble into CR2032 type button symmetric battery, and cyclic charge-discharge test is carried out on newwei battery test system.The test temperature is 25℃, the current density is 5mA·cm -2 , and the surface capacity is 1mAh·cm -2 .

[0053] Figure 4 X-ray diffraction characterization of zinc deposition can be seen that all characteristic peaks match well with the standard phase of metal zinc (PDF #78-0246), and the Zn (101) peak intensity is the highest, which shows that under the embodiment, the main crystal face of zinc ion deposition is Zn (101) crystal face perpendicular to the base face, and the formation of a small amount of byproduct Zn4SO4OH6·5 (H2O) is observed.This result shows that the hydration deep eutectic electrolyte prepared by the application can greatly inhibit the occurrence of side reaction.

[0054] Comparative example 4

[0055] At room temperature, 14.378g of zinc sulfate heptahydrate is added to 25ml of deionized water and ultrasonic for 20min to make it completely dispersed, and 25ml of electrolyte containing 2mol / L zinc sulfate is prepared, named as DES0.

[0056] Using zinc foil as positive and negative electrode, glass fiber as diaphragm, 120 μL of the above electrolyte is taken to assemble into CR2032 type button symmetric battery, and cyclic charge-discharge test is carried out on newwei battery test system.The test temperature is 25℃, the current density is 5mA·cm-2, and the surface capacity is 1mAh·cm -2 .

[0057] Figure 4 X-ray diffraction characterization of zinc deposition can be seen that all characteristic peaks match well with the standard phase of metal zinc (PDF #78-0246), and the Zn (101) peak intensity is the highest, which shows that under the embodiment, the main crystal face of zinc ion deposition is Zn (101) crystal face perpendicular to the base face, and the formation of a small amount of byproduct Zn4SO4OH6·5 (H2O) is observed.This result shows that the hydration deep eutectic electrolyte prepared by the application can greatly inhibit the occurrence of side reaction.

[0058] Example 5

[0059] A full-weather zinc-based battery hydration deep eutectic electrolyte, acetylpic acid and deionized water are mixed according to the volume ratio of 1:1, and stirred at room temperature as a solvent, then add solute zinc sulfate, make its concentration control 2mol / L, stir at room temperature for 60min, get clear and transparent electrolyte, named as DES50. The effect of acetylpic acid on inhibiting the occurrence of side reaction is verified by using the above zinc-based hydration deep eutectic electrolyte.

[0060] Using zinc foil as positive and negative electrode, glass fiber as diaphragm, taking the above electrolyte 120μL, assemble into CR2032 type button type symmetrical battery, carry out cyclic charge-discharge test on new Wei battery test system. The test temperature is 25℃, the current density is 5mA·cm -2 , the surface capacity is 1mAh·cm -2 .

[0061] Figure 5 a is the scanning electron microscope characterization of zinc deposition of example 5, it can be seen that due to the effect of directional induction of acetylpic acid, zinc ions are deposited in a layered stacking morphology parallel to the basal plane, without obvious dendrites. And a small amount of byproduct Zn4SO4OH6·5(H2O) is observed. This result shows that the hydration deep eutectic electrolyte prepared by the application can greatly inhibit the occurrence of side reaction.

[0062] Comparative example 5

[0063] At room temperature, 14.378g of zinc sulfate heptahydrate is added to 25ml of deionized water and ultrasonic for 20min to make it completely dispersed, and 25ml of electrolyte containing 2mol / L zinc sulfate is prepared, named as DES0.

[0064] Using zinc foil as positive and negative electrode, glass fiber as diaphragm, taking the above electrolyte 120μL, assemble into CR2032 type button type symmetrical battery, carry out cyclic charge-discharge test on new Wei battery test system. The test temperature is 25℃, the current density is 5mA·cm -2 , the surface capacity is 1mAh·cm -2 .

[0065] Figure 5 b is the scanning electron microscope characterization of zinc deposition of example 5, it can be seen that the zinc deposition structure of comparative example 5 is loose, with many chaotic dendrites and irregular hexagonal deposits, which may exacerbate the corrosion reaction and the accumulation of byproducts, eventually leading to battery failure, and a large amount of byproduct Zn4SO4OH6·5(H2O) is observed.

[0066] Example 6

[0067] A full-weather zinc-based battery hydration deep eutectic electrolyte, acetylpic acid and deionized water are mixed according to the volume ratio of 1:1, and stirred at room temperature as a solvent, then add solute zinc sulfate, make its concentration control 2mol / L, stirring at room temperature for 60min, get clear and transparent electrolyte, named as DES50. The effect of acetylpic acid on the capacity attenuation of full battery is verified by using the above-mentioned hydration deep eutectic electrolyte.

[0068] VOX positive electrode preparation process: dissolve vanadium oxide (V2O5, Macklin, 99%, 0.3g) in 10mL 2M sodium chloride (NaCl) aqueous solution, after continuous stirring for 72h, wash the formed orange-red gel with deionized water and ethanol several times. Then dry in a vacuum oven at 80℃ for 12 hours, take out after cooling, filter the solution, dry and grind for standby use. Take 80mg of the above prepared V2O5, mix with SuperP, polyvinylidene fluoride according to the mass ratio of 7:2:1, put in a maroon mortar and grind for 30min, add N-methyl pyrrolidone, stir for 12h, then evenly coat on the surface of titanium foil with a spatula, and slice after completely dry.

[0069] Use the above prepared VOX positive electrode material as the positive electrode, zinc foil as the negative electrode, and glass fiber as the separator, take 120μL of the above electrolyte to assemble into a CR2032 type water-based zinc ion button full battery, and perform cyclic charge-discharge test on a new battery test system. The current density is 1A·g -1 .

[0070] Comparative example 6

[0071] At room temperature, 14.378g of zinc sulfate heptahydrate is added to 25ml of deionized water and ultrasonic for 20min to make it completely dispersed, and 25ml of electrolyte containing 2mol / L zinc sulfate is prepared, named as DES0. The VOX positive electrode material prepared by the same method as example 6 is used, and another zinc foil is used as the negative electrode and glass fiber as the separator to assemble into a CR2032 type water-based zinc ion button full battery, and perform cyclic charge-discharge test on a new battery test system. The current density is 1A·g -1 .

[0072] The test results are shown in Figure 6 , the discharge specific capacity of example 6 using zinc sheet (100μm) can be maintained at 70.5% after 1000 cycles at a current density of 1A·g -1 , and the discharge specific capacity of comparative example 6 is attenuated to 35.5% after about 1000 cycles. The results show that the prepared hydration deep eutectic electrolyte can reduce the occurrence of various side reactions, maintain good electrochemical cycling performance, reduce capacity loss, and improve the reversibility of zinc deposition / stripping reaction.

[0073] Compared with the prior art, the all-weather zinc-based hydrated deep eutectic electrolyte provided by the application is formed by mixing zinc salt and hydrogen bond ligand to form a eutectic solvent, which is in a liquid state at room temperature, and the solubility of the zinc salt and the hydrogen bond ligand is improved through hydrogen bond interaction, thereby improving the conductivity of the battery and the stability of the electrolyte. Importantly, the electrolyte of the application exhibits high charge and discharge capacity and excellent cycle stability under all-weather conditions (-20℃ to 50℃), effectively expanding the working temperature range of the aqueous zinc ion battery, solving the problems of zinc negative electrode side reactions and dendrite growth at high and low temperatures, greatly prolonging the service life of the aqueous zinc ion battery, and having important significance in the field of energy storage. Moreover, the preparation method of the all-weather zinc-based hydrated deep eutectic electrolyte provided by the application is simple, fast, low in cost, safe, green and pollution-free, and is suitable for large-scale popularization and application.

[0074] Although embodiments of the application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. An all-weather zinc-based battery hydration deep eutectic electrolyte, characterized in that, The electrolyte is composed of a zinc salt, a hydrogen bond ligand and an additional aqueous solvent; The volume ratio of the water solvent and the hydrogen bond ligand is 1:1-5, and the concentration of the zinc salt in the electrolyte is maintained at 2 mol·L -1 ; The zinc salt comprises at least one of Zn(ClO4)2·6H2O, Zn(BF4)2·6H2O and ZnSO4·7H2O; The hydrogen bond ligand comprises at least one of acetyl propyl alcohol, acetyl propyl ketone and acetyl propyl acid.

2. The all-weather zinc-based battery hydration deep eutectic electrolyte according to claim 1, wherein, Preparation of all-weather zinc-based batteries.

3. An all-weather aqueous zinc-based battery, characterized in that, The all-weather zinc-based battery comprises a positive electrode, a negative electrode and the hydrated deep eutectic electrolyte of claim 1, wherein the positive electrode is prepared by loading at least one of a conductive polymer and a vanadium-based compound on a substrate.

4. The all-weather aqueous zinc-based battery of claim 3, wherein, The conductive polymer is at least one of polyaniline and polypyrrole; the vanadium-based compound is at least one of vanadium dioxide, vanadium pentoxide, sodium vanadate, basic zinc vanadate, sodium vanadate phosphate and sodium vanadate metaphosphate; the substrate is a commercially available carbon paper and an acid-etched roughened titanium foil; the loading amount of at least one of the conductive polymer and the vanadium-based compound on the substrate is 2-20 mg·cm -2 , the electrode thickness is between 0.15-1.5 mm, and the tap density is 0.6-3.5 g / cm 3 .

5. The all-weather aqueous zinc-based battery of claim 3, wherein, The loading method comprises in-situ polymerization, blade coating film formation or hydrothermal synthesis; the negative electrode is a high-purity zinc metal foil with a thickness of 10-100 μm, or a zinc thin film obtained by anodic deposition or brush coating of zinc slurry on a titanium foil, a stainless steel foil or carbon paper, with a thickness controlled at 5-30 μm.

6. The process for the preparation of an all-weather aqueous zinc-based battery according to any one of claims 3-5, characterized in that, The method comprises the following steps: assembling the positive electrode, the hydrated deep eutectic electrolyte of any one of claims 1 and the negative electrode into a water-based zinc ion battery with different device structures.

7. The all-weather aqueous zinc-based battery production method according to claim 6, wherein, The method is specifically to use glass fiber as a separator, and if a standard button shell is used to package into a button cell at a pressure of 70-90 MPa, the hydrated deep eutectic electrolyte is added in an amount of 50-100 μL.

Images