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

Abstract

The inorganic solid-state electrolyte provided in the application is prepared by heat treating organic ligands, halogen zinc salts and hydrogen halide acid in a sealed dry environment, and filtering and washing the reaction product after heat treatment to obtain halogen-based organic-coupled inorganic solid-state electrolyte material. The inorganic solid-state electrolyte provided in the application is prepared by screening organic ligands and zinc halide types and adjusting the molar ratio of the two, so as to prepare a solid-state electrolyte with high ionic conductivity, excellent thermal stability and chemical stability, good mechanical strength and a wide electrochemical window, thereby perfectly solving the side reaction at the interface between the zinc metal negative electrode and the electrolyte, and improving the electrochemical stability of the solid-state ionic battery. In addition, the application also provides a solid-state ionic battery comprising the inorganic solid-state electrolyte.

Description

TECHNICAL FIELD

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

[0002] The conversion and utilization of energy is becoming 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 are gradually becoming a strong competitor for the next generation of new energy storage systems. In addition, zinc metal has a low redox potential (-0.76 V vs. SHE) and a high theoretical specific capacity (820 mAh g -1 or 5855 mAh cm -3 ), which is suitable for use as a negative electrode for zinc ion batteries. 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 -0.296 V, which is higher than the zinc deposition potential of -0.76 V. 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. SUMMARY

[0005] 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 defect of poor stability of the current metal battery.

[0006] To solve the above problems, the application adopts the following technical solutions:

[0007] One of the purposes of the application is to provide a preparation method of inorganic solid electrolyte, comprising the following steps:

[0008] The organic ligand, halogen zinc salt and 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 comprises first heat raising treatment and then cooling treatment.

[0009] In some embodiments, the organic ligand is one or more of triazine, pyridazine, pyrazine, piperazine, pyrimidine, homopiperazine, monomethylpiperazine, dimethylpiperazine, ethylpiperazine, piperidine amine, aminotetrahydropyrrole.

[0010] In some embodiments, the halogen zinc salt is one or more of zinc fluoride salt, zinc chloride salt, zinc bromide salt, zinc iodide salt, halogen zinc salt complex zinc sulfate salt, halogen zinc salt complex trifluoromethyl zinc sulfonate salt, halogen zinc salt complex zinc nitrate salt, halogen zinc salt complex zinc perchlorate salt.

[0011] In some embodiments, the hydrogen halide acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid.

[0012] In some embodiments, the heat raising treatment specifically comprises raising the temperature to 50-200℃ at a temperature raising rate of 0.5℃min -1 -10℃min -1 , and then maintaining the temperature for 20-50h.

[0013] In some embodiments, the cooling treatment specifically comprises cooling to room temperature at a temperature lowering rate of 1℃h -1 -10℃h -1 .

[0014] In some embodiments, the filtering method comprises one or a combination of natural filtration, PTFE filtration or vacuum filtration, and the filtering material is one of PTFE, cellulose membrane and non-woven fabric, and the filtering frequency is preferably 1-5 times.

[0015] In some embodiments, the solvent used in the filtering process is one or more of water, ethanol, methanol and dimethyl sulfoxide.

[0016] The second object of the present application also provides an inorganic solid-state electrolyte prepared by the preparation method.

[0017] The second object of the present application also provides a solid-state metal ion battery comprising the inorganic solid-state electrolyte.

[0018] 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.

[0019] In some embodiments, the solid-state metal ion battery further comprises a negative electrode comprising zinc or lithium or sodium or calcium.

[0020] In some embodiments, the solid-state electrolyte has a thickness of 100-800 mu m.

[0021] The present application adopts the above technical solutions, which have the following beneficial effects:

[0022] The inorganic solid-state electrolyte provided by the present application is prepared by heat treating organic ligands, halogen zinc salts and hydrogen halide acids in a sealed 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, thereby perfectly solving 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, and has simple synthesis steps, mild conditions, low cost and strong repeatability, and can be used for large-scale preparation.

[0023] The inorganic solid-state electrolyte provided by the present application can be applied to solid-state ion batteries, achieving stable cycle performance and exhibiting broad application prospects in high-safety solid-state ion batteries. BRIEF DESCRIPTION OF DRAWINGS

[0024] 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 are only some embodiments of the present application, and those skilled in the art can obtain other drawings according to these drawings without creating any inventive labor.

[0025] Figure 1 XRD pattern of the halogen-based solid-state electrolyte sheet provided for Example 1 of the present application;

[0026] Figure 2 Electrolyte sheet and thickness test schematic of the halogen-based solid-state electrolyte provided for Example 1 of the present application;

[0027] Figure 3 Zn||Zn symmetric cell loop of the halogen-based solid-state electrolyte sheet provided for Example 3 of the present application;

[0028] Figure 4 Morphology SEM of the halogen-based solid-state electrolyte sheet provided for Example 3 of the present application facilitating zinc metal deposition. DETAILED DESCRIPTION

[0029] Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein the same or like reference numerals and characters throughout the figures denote the same or like components or elements having the same or similar functions. The embodiments described below are exemplary and intended to explain the present application, and are not intended to limit the present application.

[0030] In the description of the present application, it needs to be 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 do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application.

[0031] 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 technical features referred to. 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 "a plurality of" is two or more, unless otherwise specifically limited.

[0032] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below with reference to the drawings and examples.

[0033] An embodiment of the present application provides a preparation method of an inorganic solid-state electrolyte, comprising the following steps:

[0034] 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 heating and warming treatment and then cooling and cooling treatment. The specific implementation of the above steps is described in detail below.

[0035] In the embodiment, the organic ligand is one or more of triazine, pyridazine, pyrazine, piperazine, pyrimidine, homopiperazine, monomethylpiperazine, dimethylpiperazine, ethylpiperazine, piperidine amine, and aminotetrahydropyrrole.

[0036] 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.

[0037] 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, etc. 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.

[0038] 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.

[0039] The halogen zinc salt provided in the above embodiment is stable at room temperature, has a reasonable price, and is suitable for industrial production.

[0040] 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.

[0041] In the embodiment, the hydrogen halide acid is one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.

[0042] The hydrogen halide acid provided in the above embodiment can provide sufficient anions.

[0043] In the embodiment, the heating and warming treatment 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 h~50 h to ensure the raw materials to react sufficiently.

[0044] In this embodiment, the cooling treatment specifically includes cooling to room temperature at a cooling rate of 1℃h -1 ~10℃h -1 to ensure the synthesized crystal to precipitate with high purity and at a suitable rate.

[0045] In this 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.

[0046] In this embodiment, the filtering material is one of PTFE, cellulose membrane and non-woven fabric, and the filtering frequency is preferably 1~5 times.

[0047] It can be understood that 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 frequency is preferably 1~5 times.

[0048] In this embodiment, the solvent used in the filtering process is one or a combination of water, ethanol, methanol and dimethyl sulfoxide.

[0049] It can be understood that different washing solvents have different solubilities for the reaction raw materials, and different degrees of removal of 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.

[0050] The inorganic solid-state electrolyte provided in the present application has high ionic conductivity, low electronic conductivity, wide electrochemical window, good structural stability, etc. The inorganic solid-state electrolyte provided in the present 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.

[0051] 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.

[0052] The application also provides a solid-state metal ion battery comprising the inorganic solid-state electrolyte.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] It can be understood that by changing the type of metal ions in the solid-state electrolyte, such as replacing zinc ions with lithium ions, sodium ions, calcium ions, etc., or doping lithium ions, sodium ions, calcium ions, etc., 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, etc.), which belongs to the protection scope of the patent. In the embodiment, the thickness of the solid-state electrolyte is 100 pm to 800 pm.

[0059] 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 ~ 800 μm.

[0060] 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.

[0061] The above technical solutions of the application will be described in detail below in combination with specific embodiments.

[0062] In order to facilitate 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.

[0063] Embodiment 1

[0064] The preparation process of the novel halogen-based organic coupling inorganic solid-state electrolyte provided in this embodiment includes the following steps:

[0065] 0.3 mmol of piperazine organic ligand, 0.3 mmol of zinc bromide and 12 mmol of hydrobromic acid were put into a polytetrafluoroethylene liner tank, sealed in a stainless steel reaction kettle, placed in a blast drying oven, heated at a temperature increasing rate of 0.5 ℃ min -1 for 80 ℃ for 30 h. Then, the temperature was cooled to room temperature at a temperature decreasing rate of 2 ℃ h -1 . Then, the reaction product was washed with water and ethanol on PTFE for 3 times by suction filtration to obtain the halogen-based organic coupling inorganic solid-state electrolyte material.

[0066] The XRD of the synthesized electrolyte is shown in Figure 1 , and the materials prepared by adjusting the molar ratio of different piperazine organic ligands and zinc bromide all show similar peak positions with the standard spectrum of piperazine coupling zinc bromide (C2H 12 N2ZnBr4), which proves the successful synthesis of the material.

[0067] The solid-state electrolyte powder measured by XRD was pressed into a tablet, as shown in Figure 2 , with a diameter of 18 mm and a thickness of 590 μm.

[0068] Embodiment 2

[0069] The preparation process of the novel halogen-based organic-inorganic solid-state electrolyte provided in the embodiment comprises the following steps:

[0070] 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 are placed in a polytetrafluoroethylene liner tank, sealed in a stainless steel reaction kettle, placed in a blast drying oven, heated at a temperature increasing rate of 1 ℃ min -1 -1 to 90 ℃, and kept at 90 ℃ for 25 h. Then, the temperature is cooled to room temperature at a temperature decreasing rate of 5 ℃ h -1 -1. The reaction product is washed with water and propanol on non-woven fabric for 5 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0071] Example 3

[0072] The preparation process of the novel halogen-based organic-inorganic solid-state electrolyte provided in the embodiment comprises the following steps:

[0073] 0.1 mmol of pyrimidine, 0.1 mmol of zinc chloride salt and 3 mmol of hydrofluoric acid are placed in a polytetrafluoroethylene liner tank, sealed in a stainless steel reaction kettle, placed in a blast drying oven, heated at a temperature increasing rate of 0.5 ℃ min -1 -1 to 50 ℃, and kept at 50 ℃ for 20 h. Then, the temperature is cooled to room temperature at a temperature decreasing rate of 1 ℃ h -1 -1. The reaction product is washed with water and ethanol on PTFE for 3 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0074] Example 4

[0075] The preparation process of the novel halogen-based organic-inorganic solid-state electrolyte provided in the embodiment comprises the following steps:

[0076] 0.1 mmol of monomethyl piperazine, 0.5 mmol of halogen zinc salt and 5 mmol of hydroiodic acid are placed in a polytetrafluoroethylene liner tank, sealed in a stainless steel reaction kettle, placed in a blast drying oven, heated at a temperature increasing rate of 10 ℃ min -1 -1 to 200 ℃, and kept at 200 ℃ for 50 h. Then, the temperature is cooled to room temperature at a temperature decreasing rate of 10 ℃ h -1 -1. The reaction product is washed with water and dimethyl sulfoxide on PTFE for 5 times to obtain the halogen-based organic-inorganic solid-state electrolyte material.

[0077] Example 5

[0078] The preparation process of the novel halogen-based organic-inorganic solid-state electrolyte provided in the embodiment comprises the following steps:

[0079] 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 -1 100 ℃ for 30 h. Then cool down to room temperature at a temperature decreasing rate of 5 ℃ h -1 -1. Again, the reaction product is washed 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.

[0080] Example 6

[0081] The application of a new type of halogen-based solid-state electrolyte in high safety and long life full solid-state zinc ion secondary battery and performance test: (1) battery assembly: zinc-zinc symmetric battery, uniform zinc foil for positive and negative electrodes, and C2H 12 N2ZnBr4 prepared in Example 1 for electrolyte, assembled into CR2023 type button cell. The structure of the assembled battery is: positive shell, zinc sheet, solid-state electrolyte, zinc sheet, gasket, spring and negative shell.

[0082] (2) Electrochemical performance test: at room temperature, the assembled button cell is tested on a new Wei battery test system, and the test conditions of zinc-zinc symmetric battery are: current density is 0.5 mA cm -2 , and deposition capacity is 0.5 mAh cm -2 , and the cycle performance graph is as shown in Figure 3 Due to the large contact resistance of the solid-solid interface between the zinc electrode and the solid-state electrolyte, the zinc deposition is blocked, resulting in the gradual increase of the overpotential of the zinc-zinc symmetric battery.

[0083] (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 is disassembled, the zinc foil surface is cleaned with water, and the deposition morphology of zinc metal is observed, as shown in Figure 4 The use of solid-state electrolyte can control the deposition morphology of zinc metal and inhibit the generation of zinc dendrites.

[0084] 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 simple, 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.

[0085] 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 heat-treated in a sealed dry environment, and the reaction product after heat treatment is filtered and washed to obtain an organic-coupled inorganic solid-state electrolyte material with halogen groups, 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 a heating and warming treatment and a cooling and cooling treatment. The heating and warming treatment specifically comprises warming to 50-200℃ at a warming rate of 0.5-10℃ / min and keeping for 20-50h.

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, piperidylamine, 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 cooling treatment specifically includes cooling at a rate of 1°C / h -1 10°C / h -1 to room temperature.

6. The method for producing an inorganic solid-state electrolyte according to claim 1, wherein The filtering mode comprises one or a combination of natural filtering, PTFE filtering or vacuum suction filtering, the filtering material is one of PTFE, cellulose membrane and non-woven fabric, the filtering frequency is 1-5 times, and the washing frequency is 1-5 times.

7. The method for producing an inorganic solid-state electrolyte according to claim 6, wherein The solvent used in the filtering is one or a combination of water, ethanol, methanol and dimethyl sulfoxide.

8. An inorganic solid-state electrolyte, characterized by, Prepared by the preparation method of any one of claims 1-7.

9. A solid-state metal-ion battery, characterized by The inorganic solid-state electrolyte comprises the inorganic solid-state electrolyte of claim 8.

10. The solid-state metal-ion battery of claim 9, 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.

11. The solid-state metal-ion battery of claim 9, wherein, The solid-state metal ion battery further comprises a negative electrode comprising zinc or lithium.

12. The solid-state metal-ion battery of claim 9, wherein, The thickness of the solid-state electrolyte is 100-800μm.

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