High-voltage aqueous battery with trifunctional metal separator

Abstract

The present invention relates to a high-voltage aqueous battery with a tri-functional metal diaphragm, comprising: a positive electrode, a negative electrode, a metal diaphragm, a positive electrode electrolyte, and a negative electrode electrolyte, wherein the positive electrode and the negative electrode are separated by the metal diaphragm and are respectively in mutually independent positive electrode electrolyte and negative electrode electrolyte; in the positive electrode electrolyte, the potential of the positive electrode is greater than the potential of the metal diaphragm; in the negative electrode electrolyte, the potential of the metal diaphragm is greater than the potential of the negative electrode.

Description

Technical Field

[0001] The invention relates to a high-voltage aqueous battery with a tri-functional metal diaphragm, belonging to the technical field of secondary batteries. Background Art

[0002] Due to the current energy crisis and environmental pollution, people are turning their attention to clean and renewable energy sources such as solar, wind, and tidal energy. However, these energies are often intermittent and can only be utilized if stored. Therefore, the development of energy storage technology is imperative. Electrochemical energy storage technologies, represented by lithium-ion batteries, have attracted widespread attention due to their high energy density, mature technology, and environmental friendliness. However, lithium-ion batteries use organic electrolytes, which are prone to ignition and pose certain safety risks, making them unsuitable for large-scale power storage systems.

[0003] Aqueous batteries, which use aqueous solutions as their electrolyte, are considered the most suitable for large-scale power storage systems due to their high safety, low cost, and environmental friendliness. Despite their numerous advantages, aqueous batteries also face the challenge of low voltage. This is due to the narrow electrochemical window of water, which is only 1.23V. This severely limits the output voltage of aqueous batteries, resulting in a voltage generally below 2V, compared to the 3-4V voltage of lithium batteries. This low voltage restricts their large-scale application.

[0004] Currently, there are two main methods for increasing the voltage of aqueous batteries. One is to use high-concentration salt to reduce the electrochemical activity of water, which can successfully widen the electrochemical window of water to 3V (Suo, L.; Borodin, O.; Gao, T.; Olguin, M.; Ho, J.; Fan, X.; Luo, C.; Wang, C.; Xu, K., "Water-in-salt" electrolyte enables high-voltage aqueous lithium-ion chemistries. Science 2015, 350(6263), 938-43.). However, this method faces the problems of high cost, limited salt options, and few salts with a solubility in water exceeding 20 mol / L. Therefore, this method is not suitable for large-scale production and application. Another way is to use an acid-base mixed electrolyte and separate the acid and base electrolytes with a bipolar membrane. Since the oxygen evolution potential is higher under acidic conditions and the hydrogen evolution potential is relatively low under alkaline conditions, the electrochemical window is widened. However, this method faces the problem of mutual penetration of hydrogen ions and hydroxide ions, which makes it impossible to maintain the pH difference on both sides and the battery cycle stability is poor. Summary of the Invention

[0005] To this end, the present invention provides a high-voltage aqueous battery with a tri-functional metal separator, comprising: a positive electrode, a negative electrode, a metal separator, a positive electrode electrolyte, and a negative electrode electrolyte, wherein the positive electrode and the negative electrode are separated by the metal separator and are respectively in mutually independent positive electrode electrolyte and negative electrode electrolyte; in the positive electrode electrolyte, the potential of the positive electrode is greater than the potential of the metal separator; in the negative electrode electrolyte, the potential of the metal separator is greater than the potential of the negative electrode.

[0006] Since the oxygen evolution potential is higher in acidic electrolytes, the redox couple with higher electrode potential can be applied, and the hydrogen evolution potential is lower in alkaline electrolytes, the redox couple with lower electrode potential can be applied. Therefore, if the acidic electrolyte is combined with the alkaline electrolyte, the positive electrode is allowed to undergo electrochemical reaction in the acidic electrolyte, and the negative electrode is allowed to undergo electrochemical reaction in the alkaline electrolyte, the voltage of the battery will be improved. Currently, ion exchange membranes are commonly used to separate the two positive and negative electrolytes, but in this way, the two electrolytes still have a small number of hydrogen ions and hydroxides to penetrate each other, which causes the electrolyte pH to continuously change as the number of cycles increases, limiting the cycle stability of the battery. The inventors first used a metal diaphragm to separate the two electrolytes, so that the ion exchange of the two electrolytes is thoroughly blocked, and the cycle stability of the battery is improved.

[0007] The principle is as follows: During the charging process, under the action of the electric field, the free electrons in the metal diaphragm will gather from the negative electrode electrolyte side to the positive electrode electrolyte side, causing the metal diaphragm potential on the positive electrode side to continuously decrease compared to the positive electrode electrolyte, and the metal diaphragm potential on the negative electrode side to continuously increase compared to the negative electrode electrolyte. This causes the metal diaphragm on the positive electrode side to undergo a reduction reaction and the metal diaphragm on the negative electrode side to undergo an oxidation reaction. The discharge process is the opposite of the above-mentioned charging process. Therefore, the metal diaphragm has three functions: it can form a first battery with the negative electrode, a second battery with the positive electrode, and separate the two reacting electrolytes. The metal diaphragm potential has the following relationship with the positive and negative electrode potentials: in the negative electrode electrolyte, the negative electrode potential is less than the metal diaphragm potential; in the positive electrode electrolyte, the metal diaphragm potential is less than the positive electrode potential. Moreover, the inventors also found that "battery voltage = (positive electrode potential - negative electrode potential) + (metal diaphragm potential in negative electrode electrolyte - metal diaphragm potential in positive electrode electrolyte)", therefore, when the potential of the metal diaphragm in the negative electrode electrolyte is greater than the potential in the positive electrode electrolyte, the battery voltage can be further increased.

[0008] Preferably, the metal diaphragm is a dense metal electrode and can be a single metal such as copper, silver, lead, iron, nickel, etc.

[0009] Preferably, the negative electrode is a metallic zinc or composite zinc electrode, and the composite zinc negative electrode is a negative electrode of zinc powder or a composite of metallic zinc and carbon material.

[0010] Preferably, the positive electrode is bromine, iodine, cerium sulfate, a carbon material electrode, a manganese dioxide electrode, lead, or a lead dioxide electrode.

[0011] Preferably, the electrolyte in the negative electrode electrolyte is a zinc salt and / or an alkali, and the pH is ≥7; preferably, the zinc salt is selected from at least one of zinc acetate, zinc sulfate, zinc nitrate and zinc chloride, and the alkali is at least one of potassium hydroxide, sodium hydroxide, barium hydroxide, ammonia water and lithium hydroxide; more preferably, the concentration of the zinc salt is 0.1 to 4 mol / L (preferably 0.1 to 3 mol / L), and the concentration of the alkali is 1 to 6 mol / L.

[0012] Preferably, the electrolyte in the positive electrode electrolyte is at least one of an acid, a copper salt, a lead salt, a cerium salt, a silver salt, an iron salt, a nickel salt, a halide and a manganese salt, and the halide is at least one of sodium bromide, potassium bromide, sodium iodide and potassium iodide.

[0013] Furthermore, preferably, the acid is at least one of sulfuric acid, nitric acid and hydrochloric acid, the copper salt is at least one of copper sulfate, copper nitrate and copper acetate, the lead salt is lead nitrate, the cerium salt is at least one of ceric sulfate or ceric nitrate, the silver salt is silver nitrate, the iron salt is at least one of ferric chloride, ferric sulfate or ferric nitrate, the nickel salt is at least one of nickel sulfate or nickel nitrate, and the manganese salt is at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; preferably, the concentration of the acid is 0.1-4 mol / L, the concentration of the copper salt is 0.1-4 mol / L, the concentration of the lead salt is 0.1-4 mol / L, the concentration of the cerium salt is 0.1-4 mol / L, the concentration of the silver salt is 0.1-4 mol / L, the concentration of the iron salt is 0.1-4 mol / L, the concentration of the nickel salt is 0.1-4 mol / L, the concentration of the manganese salt is 0.1-4 mol / L, and the concentration of the halide is 0.1-4 mol / L.

[0014] Preferably, the thickness of the metal diaphragm is at least 0.1 mm; the thickness of the metal diaphragm is 0.5 to 4 times the thickness of the positive electrode.

[0015] Preferably, the high-voltage aqueous battery further comprises a first reaction chamber for accommodating a negative electrode electrolyte and a second reaction chamber for accommodating a positive electrode electrolyte, and the metal diaphragm is located between the first reaction chamber and the second reaction chamber.

[0016] Beneficial effects:

[0017] The metal diaphragm high-voltage aqueous battery designed by the present invention has universal applicability. For example, the voltage of the zinc-manganese battery designed with copper as the metal diaphragm is 1.88V, and it can be stably cycled 3,500 times. The cycle stability is better than that of the zinc-manganese battery using a bipolar membrane. The voltage of the zinc-bromine battery designed with silver as the metal diaphragm is 2.7V, which is much higher than the 1.85V of the conventional zinc-bromine battery, and it can be stably cycled 1,000 times. The voltage of the zinc-iodine battery designed with silver as the metal diaphragm is 2.4V, which is much higher than the 1.3V of the conventional zinc-iodine battery, and it can be stably cycled 800 times. The voltage of the zinc-lead battery with lead as the metal diaphragm reaches 4.2V, which is even higher than the voltage of the organic lithium-ion battery, and it can be stably cycled 300 times. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of the high-voltage aqueous zinc-manganese battery with a copper metal diaphragm of the present invention;

[0019] Figure 2 The charge and discharge curves of a high-voltage aqueous zinc-manganese battery with a copper metal separator.

[0020] Figure 3 The cycling curve of a high-voltage aqueous zinc-manganese battery with a copper metal separator.

[0021] Figure 4 This is the cycle curve of the zinc-manganese battery using bipolar membrane;

[0022] Figure 5 This is a schematic diagram of the high-voltage aqueous zinc-bromine battery with a silver metal diaphragm of the present invention;

[0023] Figure 6 The charge and discharge curves of a high-voltage aqueous zinc-bromine battery with a silver metal separator.

[0024] Figure 7 The cycling curve of a high voltage aqueous zinc-bromine battery with a silver metal separator.

[0025] Figure 8 This is a schematic diagram of the high-voltage aqueous zinc-iodine battery with a silver metal diaphragm of the present invention;

[0026] Figure 9 The charge and discharge curves of a high-voltage aqueous zinc-iodine battery with a silver metal separator.

[0027] Figure 10 The cycling curve of a high-voltage aqueous zinc-iodine battery with a silver metal separator.

[0028] Figure 11 This is a schematic diagram of the high-voltage aqueous zinc-lead battery with a lead metal separator according to the present invention;

[0029] Figure 12The charge and discharge curves of a high-voltage aqueous zinc-lead battery with a lead metal separator are shown;

[0030] Figure 13 Cycling curves of high-voltage aqueous zinc-lead batteries with lead metal separators. DETAILED DESCRIPTION

[0031] The present invention is further described below through the following embodiments. It should be understood that the following embodiments are only used to illustrate the present invention, rather than to limit the present invention.

[0032] In the present disclosure, an aqueous high-voltage battery with a trifunctional metal diaphragm is proposed, which has a higher voltage than conventional aqueous batteries and has a certain universality. The high-voltage aqueous battery with a trifunctional metal diaphragm includes: a positive electrode, a negative electrode, a negative electrode electrolyte, a positive electrode electrolyte, and a dense metal single substance diaphragm with good conductivity that can undergo reversible redox reactions in both the negative electrode electrolyte and the positive electrode electrolyte (to avoid ion exchange and mixing between the positive electrode electrolyte and the negative electrode electrolyte). The metal diaphragm includes but is not limited to metals such as copper, silver, lead, nickel, and iron. If an alloy material containing the above metals is selected, the metal diaphragm is easily corroded and penetrated due to the uncertainty of metal deposition during multiple charge and discharge reactions, resulting in a multi-pitted surface. The thickness of the metal diaphragm is at least 0.1 mm. Its thickness can be 0.5 to 4 times the thickness of the positive electrode.

[0033] In an optional embodiment, the structure of the aqueous battery includes: a negative electrode sheet made of a negative electrode located on one side of the first reaction chamber; a first reaction chamber for accommodating a negative electrode electrolyte; a second reaction chamber for accommodating a positive electrode electrolyte; a metal diaphragm located between the first reaction chamber and the second reaction chamber and used to separate the positive electrode electrolyte and the negative electrode liquid; a positive electrode sheet made of a positive electrode located on one side of the second reaction chamber; and a gasket that acts as a seal.

[0034] Among them, the negative electrode has a lower electrode potential. In the negative electrode electrolyte, the potential of the negative electrode is lower than that of the metal diaphragm, and the negative electrode and the metal diaphragm constitute the electrode material of the first battery.

[0035] The positive electrode has a higher electrode potential. In the positive electrolyte, the positive electrode's potential is higher than that of the metal separator, allowing it to form the electrode material of the second cell together with the metal separator. Furthermore, the metal separator's electrode potential in the positive electrolyte is preferably lower than that in the negative electrolyte, further increasing the battery voltage.

[0036] Among them, the negative electrode electrolyte can be an electrolyte that provides the ions required for the electrochemical reaction between the negative electrode and the metal separator, such as a neutral or alkaline electrolyte with a pH ≥ 7. Calculations based on the Nernst equation show that the concentration of the negative electrode electrolyte has little effect on the battery voltage.

[0037] Among them, the positive electrode electrolyte can be an electrolyte that provides ions required for the electrochemical reaction between the positive electrode and the metal separator, such as a neutral or acidic electrolyte (pH≤7). Calculations based on the Nernst equation show that the concentration of the positive electrode electrolyte has little effect on the battery voltage.

[0038] Among them, in addition to forming a "first battery" with the negative electrode and a "second battery" with the positive electrode, the metal separator can also play the role of separating two mutually reacting electrolytes.

[0039] In an optional embodiment, the positive electrode includes, but is not limited to, bromine, iodine, cerium sulfate, manganese dioxide, carbon materials, lead dioxide, and other active materials with a relatively high electrode potential in the positive electrode electrolyte (neutral or acidic electrolyte (pH ≤ 7)). The negative electrode may be metallic zinc, a composite zinc electrode, or other materials with a relatively low electrode potential in an alkaline or neutral electrolyte (pH ≥ 7).

[0040] The following examples are further given to illustrate the present invention in detail. It should also be understood that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above content of the present invention all fall within the scope of protection of the present invention. The specific process parameters and the like in the following examples are only examples within a suitable range, that is, those skilled in the art can make selections within a suitable range through the description herein, and are not limited to the specific numerical values exemplified below.

[0041] Example 1

[0042] Prepare a negative electrolyte containing 2.4 mol / L potassium hydroxide and 0.1 mol / L zinc acetate;

[0043] Prepare a positive electrolyte containing 1 mol / L manganese sulfate, 1 mol / L sulfuric acid, and 0.3 mol / L copper sulfate;

[0044] The battery is assembled with metal zinc as the negative electrode, carbon cloth as the positive electrode, and copper as the metal separator. The schematic diagram is as follows Figure 1 As shown, during the charging process, zinc deposition reaction occurs at the negative electrode, manganese dioxide deposition reaction occurs at the positive electrode, the copper metal diaphragm is oxidized to copper hydroxide in the negative electrode electrolyte, and copper deposition reaction occurs in the positive electrode electrolyte; during the discharging process, zinc dissolution reaction occurs at the negative electrode, manganese dioxide dissolution reaction occurs at the positive electrode, copper hydroxide reduction reaction to copper occurs in the negative electrode electrolyte of the copper metal diaphragm, and copper dissolution reaction occurs in the positive electrode electrolyte.

[0045] The assembled batteries were subjected to electrochemical tests using constant voltage charging (2.1 V) and constant current discharging (2.5 mA / cm 2 ). Figure 2This is the charge and discharge curve of the high-voltage aqueous zinc-manganese battery with a copper metal separator obtained in Example 1. It can be found that the discharge voltage platform of the battery is 1.88V, which is much higher than the voltage of existing aqueous zinc-manganese batteries.

[0046] Cycling performance of high voltage aqueous zinc-manganese battery with copper metal separator Figure 3 As shown in the figure, it can be found that the battery has excellent cycle stability. After 3500 cycles, the battery discharge capacity has almost no attenuation, and the cycle performance is better than that of the zinc-manganese battery using bipolar membrane under the same conditions ( Figure 4 ).

[0047] Example 2

[0048] Prepare a negative electrolyte containing 2.4 mol / L potassium hydroxide and 0.1 mol / L zinc acetate;

[0049] Prepare a positive electrode electrolyte containing 1 mol / L sodium bromide;

[0050] The battery is assembled with metal zinc as the negative electrode, carbon felt as the positive electrode, and silver sheet as the metal separator, as shown in the schematic diagram. Figure 5 As shown, during the charging process, zinc deposition occurs at the negative electrode, while bromide ions are oxidized to elemental bromine at the positive electrode. The silver in the negative electrolyte is oxidized to silver oxide, while the silver bromide in the positive electrolyte is reduced to silver. The discharge process is the opposite. During the first charge, hydrogen evolution occurs on the silver surface of the positive electrolyte. However, after one discharge, a layer of silver bromide forms on the surface. In subsequent cycles, a reversible conversion between silver and silver bromide occurs on the silver surface of the positive electrolyte.

[0051] The assembled batteries were subjected to electrochemical tests using constant voltage charging (3V) and constant current discharging (1mA / cm 2 ). Figure 6 The charge and discharge curves of the high-voltage aqueous zinc-bromine battery with a silver metal separator obtained in Example 1 show that the discharge voltage platform of the battery is 2.7V, which is much higher than the voltage of existing aqueous zinc-bromine batteries.

[0052] Cycling performance of high voltage aqueous zinc-bromine batteries with silver metal separators Figure 7 As shown, it can be found that the battery has excellent cycle stability, and the battery discharge capacity has almost no decay after 1000 cycles.

[0053] Example 3

[0054] Prepare a negative electrolyte containing 2.4 mol / L potassium hydroxide and 0.1 mol / L zinc acetate;

[0055] Prepare a positive electrolyte containing 1 mol / L potassium iodide;

[0056] The battery is assembled with metal zinc as the negative electrode, carbon felt as the positive electrode, and silver sheet as the metal separator, as shown in the schematic diagram. Figure 8 As shown, during the charging process, zinc deposition occurs at the negative electrode, while iodide ions oxidize to elemental iodine at the positive electrode. The silver in the negative electrolyte is oxidized to silver oxide, while the silver iodide in the positive electrolyte is reduced to silver. The discharge process is the opposite. During the first charge, hydrogen evolution occurs on the silver surface of the positive electrolyte. However, after one discharge, a layer of silver iodide forms on the surface. In subsequent cycles, a reversible conversion between silver and silver iodide occurs on the silver surface of the positive electrolyte.

[0057] The assembled batteries were subjected to electrochemical tests using constant voltage charging (2.7 V) and constant current discharging (1 mA / cm 2 ). Figure 9 This is the charge and discharge curve of the high-voltage aqueous zinc-iodine battery with a silver metal separator obtained in Example 1. It can be found that the discharge voltage platform of the battery is 2.4V, which is much higher than the voltage of existing aqueous zinc-iodine batteries.

[0058] Cycling performance of high voltage aqueous zinc-iodine batteries with silver metal separators Figure 10 As shown, it can be found that the battery has excellent cycle stability, and the battery discharge capacity has almost no decay after 800 cycles.

[0059] Example 4

[0060] Prepare a negative electrode electrolyte containing 2 mol / L zinc sulfate;

[0061] Prepare a positive electrolyte containing 4 mol / L sulfuric acid;

[0062] The battery is assembled with metal zinc as the negative electrode, lead as the positive electrode, and lead as the metal separator. The schematic diagram is as follows Figure 11 As shown, the battery needs to be activated first, and the activation method is constant current charging (15mA / cm 2 ) for 120 seconds, then discharge at a constant current (15mA / cm 2 ) until the voltage is less than 3.5V, cycle for one day, then change the charging time to 420 seconds, keep the other conditions unchanged, cycle for one day, finally change the charging time to 720 seconds, keep the other conditions unchanged, cycle for another day, so far the battery activation is complete, during the activation process a layer of lead dioxide is generated on the lead surface of the positive electrode, a layer of lead dioxide is generated on one side of the lead metal diaphragm (in the negative electrode electrolyte), and a layer of lead sulfate is generated on the other side (in the positive electrode electrolyte).

[0063] During the discharge process, zinc dissolution occurs at the negative electrode, lead dioxide is reduced to lead sulfate at the positive electrode, lead metal diaphragm undergoes lead dioxide reduction to lead sulfate in the negative electrode electrolyte, and lead is oxidized to lead sulfate in the positive electrode electrolyte. The charging process is the opposite. Figure 12The charge and discharge curve of the high voltage aqueous zinc-lead battery with lead metal separator obtained in Example 4 shows that the discharge voltage of the battery is as high as 4.2V, even higher than the voltage of organic lithium ion battery. Figure 13 As shown, the battery can be cycled stably for 300 times.

[0064] Example 5-20

[0065] The selection of the positive electrode, negative electrode, positive electrode electrolyte, negative electrode liquid and metal separator of the battery of this embodiment 5-20 is shown in Table 1, and the calculated battery voltage is also shown in Table 1.

[0066] Table 1:

[0067]

[0068]

[0069] According to Examples 1-20, when the negative electrode is zinc and the positive electrode is manganese dioxide, lead and nickel satisfy the potential in the negative electrode electrolyte > the potential in the positive electrode electrolyte, so the battery voltage exceeds the difference between the positive and negative electrode voltages (2.44V). When the negative electrode is zinc and the positive electrode is iodine, silver, lead, and nickel satisfy the potential in the negative electrode electrolyte > the potential in the positive electrode electrolyte, so the battery voltage exceeds the difference between the positive and negative electrode voltages (1.76V). When the negative electrode is zinc and the positive electrode is bromine, silver, lead, and nickel satisfy the potential in the negative electrode electrolyte > the potential in the positive electrode electrolyte, so the battery voltage exceeds the difference between the positive and negative electrode voltages (2.31V). When the negative electrode is zinc and the positive electrode is lead and lead dioxide, lead satisfies the potential in the negative electrode electrolyte > the potential in the positive electrode electrolyte, so the battery voltage exceeds the difference between the positive and negative electrode voltages (2.45V).

Claims

1. A high voltage aqueous battery with a trifunctional metal diaphragm, characterized in that: include: A positive electrode, a negative electrode, a metal separator, a positive electrode electrolyte, and a negative electrode electrolyte, wherein the positive electrode and the negative electrode are separated by the metal separator and are respectively in mutually independent positive electrode electrolyte and negative electrode electrolyte; the metal separator is a dense metal single substance separator with good conductivity that can undergo reversible redox reaction in both the negative electrode electrolyte and the positive electrode electrolyte, and is a metal single substance of copper, silver, lead, nickel or iron; the metal separator is a dense metal single substance electrode; The metal diaphragm and the negative electrode form a first battery; the metal diaphragm and the positive electrode form a second battery; and the metal diaphragm separates the positive electrode electrolyte and the negative electrode electrolyte that react with each other; The positive electrode electrolyte is a neutral or acidic electrolyte that provides the positive electrode and the metal separator with ions required for the electrochemical reaction; in the positive electrode electrolyte, the potential of the positive electrode is greater than the potential of the metal separator; the negative electrode electrolyte is a neutral or alkaline electrolyte that provides the negative electrode or the metal separator with ions required for the electrochemical reaction; in the negative electrode electrolyte, the potential of the metal separator is greater than the potential of the negative electrode; and the potential of the metal separator in the negative electrode electrolyte is greater than the potential of the metal separator in the positive electrode electrolyte; The metal separator has three functions: forming a first battery with the negative electrode, forming a second battery with the positive electrode, and separating two electrolytes that react with each other.

2. The high-voltage aqueous battery according to claim 1, characterized in that The negative electrode is a metal zinc or composite zinc electrode, wherein the composite zinc negative electrode is a negative electrode composite of zinc and carbon materials.

3. The high-voltage aqueous battery according to claim 1, wherein: The positive electrode is a bromine, iodine, cerium sulfate, carbon material, manganese dioxide, lead, or lead dioxide electrode.

4. The high-voltage aqueous battery according to claim 1, wherein: The electrolyte in the negative electrode electrolyte is zinc salt and / or alkali, and the pH value is ≥7.

5. The high-voltage aqueous battery according to claim 4, characterized in that: The zinc salt is selected from at least one of zinc acetate, zinc sulfate, zinc nitrate and zinc chloride, and the base is at least one of potassium hydroxide, sodium hydroxide and lithium hydroxide.

6. The high-voltage aqueous battery according to claim 4, characterized in that: The concentration of the zinc salt is 0.1-4 mol / L, and the concentration of the base is 1-6 mol / L.

7. The high-voltage aqueous battery according to claim 1, wherein: The electrolyte in the positive electrode electrolyte is at least one of an acid, a copper salt, a lead salt, a cerium salt, a silver salt, an iron salt, a nickel salt, a halide and a manganese salt, and the halide is at least one of sodium bromide, potassium bromide, sodium iodide and potassium iodide.

8. The high-voltage aqueous battery according to claim 7, characterized in that: The acid is at least one of sulfuric acid, nitric acid and hydrochloric acid, the copper salt is at least one of copper sulfate, copper nitrate and copper acetate, the lead salt is lead nitrate, the cerium salt is ceric sulfate, the silver salt is silver nitrate, the iron salt is at least one of ferric chloride, ferric sulfate or ferric nitrate, the nickel salt is at least one of nickel sulfate or nickel nitrate, and the manganese salt is at least one of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.

9. The high-voltage aqueous battery according to claim 7, characterized in that: The concentration of the acid is 0.1 to 4 mol / L, the concentration of the copper salt is 0.1 to 4 mol / L, the concentration of the lead salt is 0.1 to 4 mol / L, the concentration of the cerium salt is 0.1 to 4 mol / L, the concentration of the silver salt is 0.1 to 4 mol / L, the concentration of the iron salt is 0.1 to 4 mol / L, the concentration of the nickel salt is 0.1 to 4 mol / L, the concentration of the manganese salt is 0.1 to 4 mol / L, and the concentration of the halide is 0.1 to 4 mol / L.

10. The high-voltage aqueous battery according to claim 1, wherein: The thickness of the metal diaphragm is at least 0.1 mm; the thickness of the metal diaphragm is 0.5 to 4 times that of the positive electrode.

11. The high-voltage aqueous battery according to claim 1, wherein: The high-voltage aqueous battery further includes a first reaction chamber for accommodating a negative electrode electrolyte and a second reaction chamber for accommodating a positive electrode electrolyte, and the metal diaphragm is located between the first reaction chamber and the second reaction chamber.

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