Inorganic solid-state electrolyte, preparation method and solid-state metal ion battery

Abstract

Provided is an inorganic solid-state electrolyte. An organic ligand, a zinc halide, and a hydrohalic acid are subjected to heat treatment in a sealed dry environment, and the reaction product resulting from the heat treatment is filtered and washed to obtain a halogen-based organically coupled inorganic solid-state electrolyte material. With regard to the provided inorganic solid-state electrolyte, by screening the types of the organic ligand and the zinc halide and adjusting the molar ratio of the organic ligand and the zinc halide, a solid-state electrolyte having high ionic conductivity, excellent thermal stability and chemical stability, good mechanical strength, and a wide electrochemical window is prepared to perfectly solve the problem of side reactions at an interface between a zinc metal negative electrode and the electrolyte, thereby improving the electrochemical stability of a solid-state ion battery. Further provided is a solid-state ion battery comprising the inorganic solid-state electrolyte.

Description

Inorganic solid-state electrolyte, preparation method and solid-state metal ion battery TECHNICAL FIELD

[0001] The present application relates to the technical field of new energy batteries, in particular to an inorganic solid-state electrolyte, a preparation method and a solid-state metal ion battery. BACKGROUND

[0002] Under the background of the double-carbon major strategic decision of "carbon neutralization" and "carbon peak", the transformation and utilization of energy have become increasingly important, and the development of secondary batteries that can be used for large-scale energy storage is one of the future development directions. At present, the secondary battery market is mainly occupied by lithium batteries, but lithium ion batteries are difficult to meet the growing demand for large-scale distributed energy storage due to their safety and price. Zinc ion secondary batteries have the advantages of low cost, safety and environmental friendliness, and have gradually become a strong competitor for the next generation of new energy storage systems. In addition, zinc metal has a low redox potential (-0.76V vs. SHE) and a high theoretical specific capacity (820mAh g -1 or 5855mAh cm -3 ), which is suitable for use as a zinc ion battery negative electrode. At present, the electrolyte of zinc metal battery is mainly water-based electrolyte, which has high ionic conductivity and fast reaction kinetics. However, water-based electrolyte still has some serious problems, such as dendrite growth, corrosion, passivation and hydrogen evolution at the interface between the highly active zinc metal negative electrode and the electrolyte, which seriously hinders the commercialization of water-based zinc ion batteries. Therefore, it is urgent to develop alternative electrolyte systems to inhibit the side reactions at the interface between the zinc metal electrode and the water-based electrolyte.

[0003] Current zinc ion batteries are basically based on water-based electrolyte, and water-based zinc ion batteries have the advantages of high safety, good environmental friendliness and low cost. However, when the pH of the electrolyte is 5, the hydrogen evolution potential is -0.296V, which is higher than the zinc deposition potential of -0.76V. Therefore, during the electrochemical deposition process of the zinc metal negative electrode, the main solvent of the electrolyte, water, inevitably decomposes, making the interface between the zinc metal negative electrode and the water-based electrolyte prone to serious zinc dendrite, hydrogen evolution, corrosion and passivation side reactions, especially at low current density, the side reactions at the interface are more serious, which will not be conducive to the development and application of water-based zinc ion batteries.

[0004] Therefore, it is urgent to develop a new type of zinc ion battery with high stability to solve the side reactions at the interface between the zinc metal negative electrode and the electrolyte and improve the stability of the zinc metal battery.

[0005] SUMMARY

[0006] In view of this, it is necessary to provide an inorganic solid-state electrolyte with high stability, a preparation method and a solid-state metal ion battery to solve the technical defects of poor stability of current metal batteries.

[0007] To solve the above problems, the technical scheme is adopted in the present application:

[0008] One of the purposes of the present application is to provide a preparation method of an inorganic solid-state electrolyte, comprising the following steps:

[0009] The organic ligand, halogen zinc salt and hydrogen halide acid are heat treated in a sealed and dry environment, and the reaction product after heat treatment is filtered and washed to obtain a halogen-based organic-coupled inorganic solid-state electrolyte material, the molar ratio of the organic ligand, the halogen zinc salt and the hydrogen halide acid is 1:(1-5):(30-50), and the heat treatment comprises first heat raising treatment and then cooling treatment.

[0010] In some embodiments, the organic ligand is one or more of triazine, pyridazine, pyrazine, piperazine, pyrimidine, homopiperazine, monomethylpiperazine, dimethylpiperazine, ethylpiperazine, piperidine amine, and aminotetrahydropyrrole.

[0011] In some embodiments, the halogen zinc salt is one or more of a zinc fluoride salt, a zinc chloride salt, a zinc bromide salt, a zinc iodide salt, a halogen zinc salt complex zinc sulfate salt, a halogen zinc salt complex trifluoromethyl zinc sulfate salt, a halogen zinc salt complex zinc nitrate salt, and a halogen zinc salt complex zinc perchlorate salt.

[0012] In some embodiments, the hydrogen halide acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid.

[0013] In some embodiments, the heat raising treatment specifically comprises raising the temperature to 50-200°C at a temperature raising rate of 0.5°C / min -1 -10°C / min -1 , and then maintaining the temperature for 20-50h.

[0014] In some embodiments, the cooling treatment specifically comprises cooling to room temperature at a temperature lowering rate of 1°C / h -1 -10°C / h -1 .

[0015] In some embodiments, the filtering method comprises one or a combination of natural filtration, PTFE filtration or vacuum filtration, the filtering material is one of PTFE, cellulose membrane and non-woven fabric, and the number of filtration is preferably 1-5 times.

[0016] In some embodiments, the solvent used in the filtering is one or more of water, ethanol, methanol, dimethyl sulfoxide.

[0017] The second object of the present application also provides an inorganic solid-state electrolyte prepared by the preparation method.

[0018] The second object of the present application also provides a solid-state metal ion battery comprising the inorganic solid-state electrolyte.

[0019] In some embodiments, the solid-state metal ion battery further comprises a positive electrode comprising manganese dioxide, vanadium pentoxide, ammonium vanadate, cobalt-nickel sulfide, elemental iodine or elemental bromine.

[0020] In some embodiments, the solid-state metal ion battery further comprises a negative electrode comprising zinc or lithium or sodium or calcium.

[0021] In some embodiments, the solid-state electrolyte has a thickness of 100-800 μm.

[0022] The present application adopts the above technical solution, which has the following beneficial effects:

[0023] The inorganic solid-state electrolyte provided by the present application is prepared by heat treating organic ligands, halogen zinc salts and hydrogen halide acid in a sealed and dry environment, and filtering and washing the reaction product after heat treatment to obtain a halogen-based organic-coupled inorganic solid-state electrolyte material. The inorganic solid-state electrolyte provided by the present application has high ionic conductivity, excellent thermal stability and chemical stability, good mechanical strength and a wide electrochemical window by screening the types of organic ligands and zinc halides and adjusting the molar ratio of the two, which perfectly solves the side reactions at the interface between the zinc metal negative electrode and the electrolyte, thereby improving the electrochemical stability of the solid-state ion battery. In addition, the inorganic solid-state electrolyte provided by the present application uses organic ligands to increase the lattice spacing of halogen-based zinc salts, thereby widening the migration path of Zn 2+ ions in the solid-state electrolyte. Furthermore, the inorganic solid-state electrolyte provided by the present application can provide a series of halogen-based solid-state electrolytes with specific functions for solid-state metal ion batteries, which has simple synthesis steps, mild conditions, low cost and strong repeatability, and can be used for large-scale preparation.

[0024] The inorganic solid-state electrolyte provided by the present application can be applied to a solid-state ion battery, realizes stable cycle performance, and has a broad application prospect in high-safety solid-state ion batteries. BRIEF DESCRIPTION OF DRAWINGS

[0025] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments of the present application or the prior art description. Obviously, the drawings described below only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained without creative labor on the basis of these drawings.

[0026] FIG. 1 is an XRD diagram of a halogen-based solid-state electrolyte sheet provided by an embodiment of the present application;

[0027] FIG. 2 is an electrolyte sheet and thickness test schematic diagram of a halogen-based solid-state electrolyte provided by an embodiment of the present application;

[0028] FIG. 3 is a Zn||Zn symmetric cell loop diagram of a halogen-based solid-state electrolyte sheet provided by an embodiment of the present application;

[0029] FIG. 4 is a morphology SEM diagram of a halogen-based solid-state electrolyte sheet provided by an embodiment of the present application to promote zinc metal deposition. DETAILED DESCRIPTION

[0030] The embodiments of the present application will be described in detail below, examples of which are shown in the drawings, wherein the same or similar notations represent the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0031] In the description of the present application, it is understood that the terms "upper", "lower", "horizontal", "inner", "outer" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the indicated device or element must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation of the present application.

[0032] In addition, the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features. In the description of the present application, the meaning of "multiple" is two or more, unless otherwise specifically limited.

[0033] In order to make the purpose, technical solutions and advantages of the present application more clear, the following will further describe the present application in combination with the drawings and embodiments.

[0034] An embodiment of the present application provides a preparation method of an inorganic solid-state electrolyte, comprising the following steps:

[0035] The organic ligand, the halogen zinc salt and the hydrogen halide acid are heat treated in a sealed dry environment, and the reaction product after heat treatment is filtered and washed to obtain a halogen-based organic-coupled inorganic solid electrolyte material, the molar ratio of the organic ligand, the halogen zinc salt and the hydrogen halide acid is 1:(1-5):(30-50), and the heat treatment includes first heating and then cooling.

[0036] In the embodiment, the organic ligand is one or more of triazine, pyridazine, pyrazine, piperazine, pyrimidine, homopiperazine, monomethylpiperazine, dimethylpiperazine, ethylpiperazine, piperidine amine, and aminotetrahydropyrrole.

[0037] It can be understood that the organic ligand provided in the above embodiment has stable structure, appropriate size and can lose electrons to show positive valence in the preparation process, which not only ensures that the small molecule has the characteristics of losing 2 electrons in the preparation process, but also the size of the molecular structure can be embedded in the crystal lattice of the halogen zinc salt and can maintain the high stability of the halogen zinc salt structure.

[0038] It should be noted that the organic ligand provided in the above embodiment is not limited to the above-mentioned substances, and in practice, the oxazines can be replaced by sulfones, imides, ethers and the like. Moreover, by changing the type of organic ligand, the crystal lattice spacing of the inorganic salt can be accurately controlled according to the needs, so as to improve the ion conduction rate to meet different application scenarios.

[0039] In the embodiment, the halogen zinc salt is one or more of a zinc fluoride salt, a zinc chloride salt, a zinc bromide salt, a zinc iodide salt, a halogen zinc salt complex zinc sulfate salt, a halogen zinc salt complex trifluoromethyl zinc sulfate salt, a halogen zinc salt complex zinc nitrate salt, and a halogen zinc salt complex zinc perchlorate salt.

[0040] The halogen zinc salt provided in the above embodiment is stable at room temperature, has a reasonable price and is suitable for industrial production.

[0041] It should be noted that the type of halogen in the above halogen-based halogen can be changed, such as expanding single halogen to dihalogen, trihalogen or multi-halogen material mixture, to adapt to different application requirements.

[0042] In the embodiment, the hydrogen halide acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.

[0043] The hydrogen halide acid provided in the above embodiment can provide sufficient anions.

[0044] In the embodiment, the heating and temperature raising process specifically includes heating at a rate of 0.5℃ / min -1 ~10℃ / min -1The temperature rising rate is rising to 50-200℃, and then keeping the temperature for 20-50h to ensure the raw materials to react sufficiently.

[0045] In the embodiment, the cooling treatment specifically includes cooling to room temperature at a cooling rate of 1-10℃ / h to ensure the synthesized crystal to precipitate at a high purity and a suitable rate. -1 -1 The temperature rising rate is rising to 50-200℃, and then keeping the temperature for 20-50h to ensure the raw materials to react sufficiently.

[0046] In the embodiment, the filtering mode includes one or a combination of natural filtering, PTFE filtering or vacuum filtration. It can be understood that, due to the different nucleation sizes of the reaction products at different cooling rates after the reaction, in order to screen halogen-based materials with uniform particle size, the filtering mode of the reaction product after the reaction is preferably natural filtering, PTFE filtering or vacuum filtration.

[0047] In the embodiment, the filtering material is one of PTFE, cellulose membrane and non-woven fabric, and the filtering times are preferably 1-5 times.

[0048] It can be understood that different filters of different materials have different pore sizes, which can screen halogen-based materials of different sizes, and the more the screening times, the better the uniformity of the prepared halogen-based solid electrolyte. The filtering material is preferably PTFE, cellulose membrane and non-woven fabric, and the filtering times are preferably 1-5 times.

[0049] In the embodiment, the solvent used in the filtering is one or a combination of water, ethanol, methanol and dimethyl sulfoxide.

[0050] It can be understood that different washing solvents have different solubilities for the reaction raw materials, and different degrees of removing unreacted reactants in the reaction product, resulting in different purities of the prepared halogen-based materials. The filtering and washing solvent is preferably one or a combination of water, ethanol, methanol and dimethyl sulfoxide.

[0051] The inorganic solid electrolyte provided by the application has high ionic conductivity, low electronic conductivity, wide electrochemical window, good structural stability, etc. The inorganic solid electrolyte provided by the application is preferably one or a combination of pure zinc fluoride and triazine coupling, pure zinc chloride and piperazine coupling, pure zinc bromide and triazine coupling, pure zinc bromide and piperazine coupling, binary hybrid of zinc fluoride and triazine coupling and zinc chloride and piperazine coupling, binary hybrid of zinc bromide and triazine coupling and zinc chloride and piperazine coupling, ternary hybrid of zinc chloride and piperazine coupling and zinc fluoride and triazine coupling and zinc bromide and piperazine coupling, etc.

[0052] ​The inorganic solid-state electrolyte provided in the application solves the side reaction at the interface between the zinc metal negative electrode and the electrolyte by preparing a solid-state electrolyte with high ionic conductivity, excellent thermal stability and chemical stability, good mechanical strength and a wide electrochemical window, thereby improving the electrochemical stability of the solid-state ionic battery. 2+ The inorganic solid-state electrolyte provided in the application can provide a series of halogen-based solid-state electrolytes with specific functions for solid-state metal ion batteries, and has the advantages of simple synthesis steps, mild conditions, low cost and strong repeatability, and can be used for large-scale preparation.

[0053] The application also provides a solid-state metal ion battery comprising the inorganic solid-state electrolyte.

[0054] The halogen-based organic-inorganic solid-state electrolyte prepared in the application not only has the advantages of high ionic conductivity, low electronic conductivity, wide electrochemical window, good structural stability, low cost, easy preparation and strong repeatability, but also perfectly solves the side reaction at the interface between the solid-state electrolyte and the zinc metal electrode, thereby improving the electrochemical stability of the solid-state zinc ion secondary battery.

[0055] It can be understood that one or more of powder pressing method, coating method and the like can be used to prepare the above-mentioned solid-state electrolyte, which is simple to operate, can be prepared on a large scale, and has strong sample uniformity.

[0056] In the embodiment, the solid-state metal ion battery further comprises a positive electrode, and the positive electrode comprises manganese dioxide, vanadium pentoxide, ammonium vanadate, cobalt-nickel sulfide, elemental iodine or elemental bromine.

[0057] It can be understood that the positive electrode of the solid-state metal ion battery provided in the embodiment has stable structure, low cost and easy-to-synthesize material, and can be suitable for industrial production.

[0058] In the embodiment, the solid-state metal ion battery further comprises a negative electrode, and the negative electrode comprises zinc or lithium or sodium or calcium.

[0059] It can be understood that by replacing or doping lithium ions, sodium ions, calcium ions and the like with zinc ions in the metal ions in the solid-state electrolyte, the technical scheme of the application can be applied to other fields of solid-state metal ion batteries (such as solid-state lithium ion batteries, solid-state sodium ion batteries, solid-state calcium ion batteries and the like), which belongs to the protection scope of the patent. In the embodiment, the thickness of the solid-state electrolyte is 100-800 mu m.

[0060] It should be noted that the thickness of the solid-state electrolyte seriously affects the ion conduction rate, and too thick electrolyte is easy to cause large resistance and slow ion transmission, and too thin electrolyte is easy to be broken, and the thickness of the solid-state electrolyte is preferably 100 μm to 800 μm.

[0061] The inorganic solid-state electrolyte prepared in the application can be applied to a solid-state ion battery, realizes stable cycle performance, suppresses the side reaction between the metal negative electrode and the electrolyte interface in the solid-state ion battery, and has a broad application prospect in the high-safety solid-state ion battery.

[0062] The above technical solutions of the application will be described in detail below in combination with specific embodiments.

[0063] In order to facilitate the understanding of the application, the technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0064] Embodiment 1

[0065] The preparation process of the novel halogen-based organic coupling inorganic solid-state electrolyte provided in this embodiment includes the following steps:

[0066] 0.3 mmol of piperazine organic ligand, 0.3 mmol of zinc bromide and 12 mmol of hydrobromic acid were placed in a polytetrafluoroethylene liner tank, sealed in a stainless steel reaction kettle, placed in a forced air drying oven, heated at a heating rate of 0.5 ℃min -1 -1 to 80 ℃, and kept at 80 ℃ for 30 h. Then, the temperature was cooled to room temperature at a cooling rate of 2 ℃h -1 -1. The reaction product was then washed with water and ethanol on PTFE by suction filtration for 3 times to obtain the halogen-based organic coupling inorganic solid-state electrolyte material.

[0067] The XRD of the synthesized electrolyte is shown in Fig. 1, and the materials prepared by adjusting the molar ratio of different piperazine organic ligands and zinc bromide all exhibit similar peak positions to the standard spectrum of piperazine coupling zinc bromide (C2H 12 N2ZnBr4), proving the successful synthesis of the material.

[0068] The solid-state electrolyte powder measured by XRD was pressed into a tablet, as shown in Fig. 2, with a diameter of 18 mm and a thickness of 590 μm.

[0069] Embodiment 2

[0070] The preparation process of the novel halogen-based organic coupling inorganic solid-state electrolyte provided in this embodiment includes the following steps:

[0071] Put 0.6 mmol of pyridazine, 0.3 mmol of piperazine, 0.6 mmol of zinc chloride, 0.3 mmol of zinc bromide, 30 mmol of hydrochloric acid and 15 mmol of hydrobromic acid into a polytetrafluoroethylene lined jar, seal in a stainless steel autoclave, and place in a forced air drying oven, and heat at a rate of 1 °C min -1 -1 to 90 °C, and hold at 90 °C for 25 h. Then cool at a rate of 5 °C h -1 -1 to room temperature. Then wash the reaction product on non-woven cloth with water and propanol for 5 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0072] Example 3

[0073] The preparation process of a new halogen-based organic-inorganic solid-state electrolyte provided in this example includes the following steps:

[0074] Put 0.1 mmol of pyrimidine, 0.1 mmol of zinc chloride salt and 3 mmol of hydrofluoric acid into a polytetrafluoroethylene lined jar, seal in a stainless steel autoclave, and place in a forced air drying oven, and heat at a rate of 0.5 °C min -1 -1 to 50 °C, and hold at 50 °C for 20 h. Then cool at a rate of 1 °C h -1 -1 to room temperature. Then wash the reaction product on PTFE with water and ethanol by suction filtration for 3 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0075] Example 4

[0076] The preparation process of a new halogen-based organic-inorganic solid-state electrolyte provided in this example includes the following steps:

[0077] Put 0.1 mmol of monomethyl piperazine, 0.5 mmol of halogen zinc salt and 5 mmol of zinc sulfate salt into a polytetrafluoroethylene lined jar, seal in a stainless steel autoclave, and place in a forced air drying oven, and heat at a rate of 10 °C min -1 -1 to 200 °C, and hold at 200 °C for 50 h. Then cool at a rate of 10 °C h -1 -1 to room temperature. Then wash the reaction product on PTFE with water and dimethyl sulfoxide by suction filtration for 5 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0078] Example 5

[0079] The preparation process of a new halogen-based organic-inorganic solid-state electrolyte provided in this example includes the following steps:

[0080] Put 0.2 mmol of piperidine amine, 0.8 mmol of halogen zinc salt complex zinc nitrate salt and 8 mmol of hydrofluoric acid into a polytetrafluoroethylene lined tank, seal in a stainless steel reaction kettle, place in a blast drying oven, heat at a temperature increasing rate of 5 ℃ / min -1 to 100 ℃ for 30 h. Then cool down to room temperature at a temperature decreasing rate of 5 ℃ / h -1 . Then wash the reaction product with water and methanol on a cellulose membrane by suction filtration for 5 times to obtain a halogen-based organic-inorganic solid-state electrolyte material.

[0081] Example 6

[0082] The application of a new type of halogen-based solid-state electrolyte in a high-safety and long-life all-solid-state zinc ion secondary battery and performance testing: (1) battery assembly: zinc-zinc symmetric battery, uniform zinc foil for both positive and negative electrodes, and C2H 12 N2ZnBr4 prepared in Example 1 as the electrolyte, assembled into a CR2023 type button cell. The structure of the assembled battery is: positive electrode shell, zinc sheet, solid-state electrolyte, zinc sheet, gasket, spring and negative electrode shell.

[0083] (2) Electrochemical performance test: at room temperature, the assembled button cell was tested for charge and discharge on a new wei battery test system. The test conditions of the zinc-zinc symmetric battery were: current density was 0.5 mA / cm -2 , and deposition capacity was 0.5 mAh / cm -2 . The cycle performance chart is shown in Figure 3. Due to the large solid-solid interface contact resistance between the zinc electrode and the solid-state electrolyte, the zinc deposition was blocked, resulting in a gradual increase in the overpotential of the zinc-zinc symmetric battery.

[0084] (3) Observation of zinc deposition morphology after cycling: after 10 cycles at 0.5 mA / cm -2 and 0.5 mAh / cm -2 at room temperature, the battery was disassembled, the zinc foil surface was washed with water, and the deposition morphology of zinc metal was observed, as shown in Figure 4, which was uniform spherical deposition. The use of solid-state electrolyte can control the deposition morphology of zinc metal and inhibit the generation of zinc dendrites.

[0085] It can be understood that any combination of the technical features of the above-described embodiments can be made. In order to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, however, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present disclosure.

[0086] The above merely describes preferred embodiments of the present application, and only specifically describes the technical principles of the present application, and these descriptions are only for explaining the principles of the present application, and cannot be explained as limitations on the protection scope of the present application in any way. Based on the explanations here, any modifications, equivalent replacements and improvements made within the spirit and principles of the present application, and other specific embodiments of the present application that can be thought of by those skilled in the art without creative labor, should be included in the protection scope of the present application.

Claims

1. A method for producing an inorganic solid-state electrolyte, characterized by, The method comprises the following steps: The organic ligand, the halogen zinc salt and the hydrogen halide acid are heated in a sealed dry environment, and the reaction product after the heating is filtered and washed to obtain an organic-coupled inorganic solid electrolyte material with halogen groups, the molar ratio of the organic ligand, the halogen zinc salt and the hydrogen halide acid being 1:(1-5):(30-50), and the heating including a heating and warming process followed by a cooling and cooling process.

2. The method for producing an inorganic solid-state electrolyte according to claim 1, wherein The organic ligand is one or more of triazine, pyridazine, pyrazine, piperazine, pyrimidine, homopiperazine, monomethylpiperazine, dimethylpiperazine, ethylpiperazine, piperidine amine, aminotetrahydropyrrole.

3. The method for producing an inorganic solid-state electrolyte according to claim 1, wherein The halogen zinc salt is one or more of a zinc fluoride salt, a zinc chloride salt, a zinc bromide salt, a zinc iodide salt, a halogen zinc salt complex zinc sulfate salt, a halogen zinc salt complex trifluoromethyl zinc sulfate salt, a halogen zinc salt complex zinc nitrate salt, and a halogen zinc salt complex zinc perchlorate salt.

4. The method for producing an inorganic solid-state electrolyte according to claim 1, wherein The hydrogen halide acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, and hydroiodic acid.

5. The method for preparing the inorganic solid electrolyte as described in claim 1, characterized in that, The heating and temperature raising treatment specifically includes temperature raising to 50°C to 200°C at a temperature raising rate of 0.5°C / min -1 to 10°C / min, and then keeping at the temperature for 20 h to 50 h. -1 The heating and temperature raising treatment specifically includes temperature raising to 50°C to 200°C at a temperature raising rate of 0.5°C / min -1 to 10°C / min, and then keeping at the temperature for 20 h to 6. The method for producing an inorganic solid-state electrolyte according to claim 1, wherein The cooling treatment specifically includes cooling at a cooling rate of 1°C / h -1 ~ 10°C / h -1 to room temperature.

7. The method of claim 1, wherein the inorganic solid-state electrolyte is prepared by a process comprising: preparing a precursor solution by dissolving a lithium salt in a solvent; and preparing the inorganic solid-state electrolyte by mixing the precursor solution with a polymer solution. The filtering method includes one or a combination of natural filtering, PTFE filtering, or vacuum filtration, and the filtering material is one of PTFE, cellulose membrane, and non-woven fabric, and the number of filtering is preferably 1-5 times.

8. The method for producing an inorganic solid-state electrolyte according to claim 7, wherein The solvent used in the filtering is one or more of water, ethanol, methanol, and dimethyl sulfoxide.

9. An inorganic solid-state electrolyte, characterized by, The method is prepared by any one of claims 1-8.

10. A solid-state metal-ion battery, characterized by The inorganic solid electrolyte is prepared by the method of claim 9.

11. The solid-state metal-ion battery of claim 10, wherein, The solid-state metal ion battery further comprises a positive electrode comprising manganese dioxide, vanadium pentoxide, ammonium vanadate, cobalt-nickel sulfide, elemental iodine, or elemental bromine.

12. The solid-state metal-ion battery of claim 10, wherein, The solid-state metal ion battery further comprises a negative electrode comprising zinc or lithium.

13. The solid-state metal-ion battery of claim 10, wherein, The thickness of the solid-state electrolyte is 100-800 μm. The thickness of the solid-state electrolyte is 100-800 μm.

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