阅读说明：本技术 一种固态电解质材料及其制备方法和应用 (Solid electrolyte material and preparation method and application thereof ) 是由 周宇楠 陈少杰 曹晓菊 刘景超 黄海强 李瑞杰 王磊 李生 袁文森 王志文 张琪 于 2021-09-13 设计创作，主要内容包括：本发明涉及锂电池技术领域,具体而言,涉及一种固态电解质材料及其制备方法和应用。本发明的固态电解质材料包括Li-(a)A-(1-x)M-(1.5x)Cl-(a+3)；其中,A包括In和/或Sc,M包括Cu、Zn、Cd、Mg和Ca中的至少一种；1.5≤a≤4.5,0.1≤x≤0.9。本发明的固态电解质材料具有尖晶石型结构,可实现电极材料氧化电位的提升,提高正极侧的电化学稳定性和化学稳定性,提升电池的初始容量发挥和循环稳定性。(The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte material and a preparation method and application thereof. The solid electrolyte material of the present invention includes Li a A 1‑x M 1.5x Cl a+3 (ii) a Wherein, A bagThe material comprises In and/or Sc, and M comprises at least one of Cu, Zn, Cd, Mg and Ca; a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9. The solid electrolyte material has a spinel structure, can realize the improvement of the oxidation potential of an electrode material, improves the electrochemical stability and the chemical stability of a positive electrode side, and improves the initial capacity exertion and the cycling stability of a battery.)

1. A solid state electrolyte material, characterized in that the solid state electrolyte material comprises Li_aA_1-xM_1.5xCl_a+3(ii) a Wherein, A comprises In and/or Sc, and M comprises at least one of Cu, Zn, Cd, Mg and Ca; a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9.

2. The solid state electrolyte material according to claim 1, characterized in that the M is selected from at least one of Mg, Cu, and Zn;

and/or a is more than or equal to 2 and less than or equal to 4, and x is more than or equal to 0.1 and less than or equal to 0.6.

3. The solid state electrolyte material of claim 1, wherein the solid state electrolyte material is a glass-ceramic phase or a crystalline phase;

preferably, the crystal structure of the solid electrolyte material is a spinel structure.

4. The solid electrolyte material according to claim 1, characterized in that the solid electrolyte material is prepared from raw materials including a precursor of lithium, a precursor of a, and a precursor of M;

preferably, the lithium precursor comprises lithium chloride;

preferably, the precursor of A comprises the chloride corresponding to A;

preferably, the precursor of M comprises the chloride corresponding to M;

preferably, the mass ratio of the lithium chloride to the chloride corresponding to A to the chloride corresponding to M is 1 (1.785-13.044) to (0.056-0.965).

5. The method for producing a solid electrolyte material according to any one of claims 1 to 4, comprising the steps of:

and calcining the mixture of the lithium precursor, the precursor of A and the precursor of M under the condition of inert gas.

6. The method for producing a solid electrolyte material according to claim 5, characterized in that the calcination includes: heating the temperature from room temperature to 300-600 ℃, preserving the heat at the temperature of 300-600 ℃, and then cooling the preserved heat to room temperature;

preferably, the heating rate of the heating to the temperature of 300-600 ℃ is 1.8-2.2 ℃/min;

preferably, the heat preservation time is 1-40 h;

preferably, the cooling rate of the temperature to the room temperature is 1.8-2.2 ℃/min.

7. The method for producing a solid electrolyte material according to claim 5, characterized by further comprising, before the calcining: performing first grinding on the mixture, and then performing tabletting;

preferably, the first grinding time is 25-35 min.

8. The method of producing a solid electrolyte material according to claim 5, characterized in that the calcined mixture is subjected to second grinding;

preferably, the time of the second grinding is 25-35 min.

9. A lithium secondary battery comprising the solid electrolyte material according to any one of claims 1 to 4.

10. The lithium secondary battery according to claim 9, wherein the lithium secondary battery comprises a positive electrode, a negative electrode, and an electrolyte layer; at least one of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material.

Technical Field

The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte material and a preparation method and application thereof.

Background

Since sony introduced lithium ion batteries in 1991, it has been widely used in various portable electronic products (such as notebook computers, mobile phones, and digital cameras), electric vehicles, and other fields. Because the traditional lithium ion battery needs to use flammable organic solvent as electrolyte, potential safety hazards exist, and the problem cannot be thoroughly solved by adopting a common improvement method. In contrast, solid-state lithium ion batteries using solid-state electrolytes have a safety advantage. The solid electrolyte is adopted, so that the safety problem of the lithium ion battery can be fundamentally solved, the manufacturing and packaging process is expected to be greatly simplified, and the energy density, reliability and design freedom of the battery are improved. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industry, which has become a consensus of the industry and the scientific community. In order to meet the requirement of high energy density, the cathode material is usually matched with a high-potential ternary cathode material, so that a strong requirement is put on the high-potential stability (>4V) of the electrolyte.

Among inorganic electrolyte materials, oxide electrolytes have high oxidation potential and are stable to high-voltage ternary cathode materials; however, the oxide electrolyte material is difficult to achieve high ionic conductivity, and has high rigidity and poor ductility, resulting in high contact resistance with the positive electrode material. In contrast, sulfide systems generally have high ionic conductivity, good ductility, and can form relatively dense physical contact with the positive electrode material; however, the raw material cost of sulfide is high, the preparation conditions are harsh, the oxidation potential is low (generally <3V), and serious side reactions occur in the circulation process when the sulfide is in direct contact with the cathode material. In addition, the halide electrolyte material is a solid electrolyte material which is recently focused, and has many advantages of high ionic conductivity, good ductility and the like. However, the monoclinic halide electrolyte in the prior art cannot meet the requirement of higher oxidation potential (reaching more than 4.5V), or needs to be prepared under the conditions of high temperature and long time, and has larger energy consumption.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a solid electrolyte material to solve the problems that a monoclinic halide electrolyte in the prior art cannot meet the requirement of higher oxidation potential (more than 4.5V), or needs to be prepared by reaction at high temperature for a long time, and has higher energy consumption. The solid electrolyte material can realize the improvement of the oxidation potential of the material, improve the electrochemical stability and the chemical stability of the positive electrode side, and improve the initial capacity exertion and the cycling stability of the battery.

The invention also aims to provide a preparation method of the solid electrolyte material, which is mild in condition, simple and feasible.

It is another object of the present invention to provide a lithium secondary battery comprising the solid electrolyte material as described above. The solid electrolyte material of the present invention can impart excellent initial capacity exertion and cycle stability to a lithium secondary battery.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

a solid state electrolyte material comprising Li_aA_1-xM_1.5xCl_a+3(ii) a Wherein, A comprises In and/or Sc, and M comprises at least one of Cu, Zn, Cd, Mg and Ca; a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9.

Preferably, the M is selected from at least one of Mg, Cu and Zn;

and/or a is more than or equal to 2 and less than or equal to 4, and x is more than or equal to 0.1 and less than or equal to 0.6.

Preferably, the solid electrolyte material is a glass-ceramic phase or a crystalline phase;

preferably, the crystal structure of the solid electrolyte material is a spinel structure.

Preferably, the solid electrolyte material is prepared from raw materials including a precursor of lithium, a precursor of a, and a precursor of M;

preferably, the lithium precursor comprises lithium chloride;

preferably, the precursor of A comprises the chloride corresponding to A;

preferably, the precursor of M comprises the chloride corresponding to M;

preferably, the mass ratio of the lithium chloride to the chloride corresponding to A to the chloride corresponding to M is 1 (1.785-13.044) to (0.056-0.965).

The method for producing a solid electrolyte material as described above, comprising the steps of:

and calcining the mixture of the lithium precursor, the precursor of A and the precursor of M under the condition of inert gas.

Preferably, the calcining comprises: heating the temperature from room temperature to 300-600 ℃, preserving the heat at the temperature of 300-600 ℃, and then cooling the preserved heat to room temperature;

preferably, the heating rate of the heating to the temperature of 300-600 ℃ is 1.8-2.2 ℃/min;

preferably, the heat preservation time is 1-40 h;

preferably, the cooling rate of the temperature to the room temperature is 1.8-2.2 ℃/min.

Preferably, the calcining further comprises: performing first grinding on the mixture, and then performing tabletting;

preferably, the first grinding time is 25-35 min.

Preferably, the calcined mixture is subjected to a second grinding;

preferably, the time of the second grinding is 25-35 min.

A lithium secondary battery comprising the solid electrolyte material as described above;

preferably, the lithium secondary battery includes a positive electrode, a negative electrode, and an electrolyte layer; at least one of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material.

Compared with the prior art, the invention has the beneficial effects that:

(1) the solid electrolyte material has a spinel structure, can realize the improvement of the oxidation potential of the material, improves the electrochemical stability and the chemical stability of the positive electrode side, improves the initial capacity exertion and the cycling stability of the battery, and improves the application possibility of the solid battery.

(2) The preparation method of the solid electrolyte material has mild conditions and is simple and feasible.

(3) The lithium secondary battery prepared by the solid electrolyte material has excellent initial capacity exertion and cycling stability.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

Fig. 1 is an XRD pattern of the solid electrolyte material in example 1;

fig. 2 is an XRD pattern of the solid electrolyte material in comparative example 1.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

According to one aspect of the invention, the invention relates to a solid state electrolyte material comprising Li_aA_1-xM_1.5xCl_a+3(ii) a Wherein, A comprises In and/or Sc, and M comprises at least one of Cu, Zn, Cd, Mg and Ca; a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9.

According to the invention, divalent ions are introduced into electrolyte components at the same time, quantitative doping regulation and control are carried out, the oxidation potential of the halide electrolyte material can be obviously improved, and the principle is as follows: by utilizing the valence state and radius difference between the divalent ion and the trivalent ion, the divalent ion doping can cause the number of lithium ions and holes in crystal lattices to change, and can cause the octahedron formed by cations and anions to generate distortion change, and Li is promoted to generate under the action of the distortion force₃InCl₆And Li₃ScCl₆The space group of C2/m is converted into the space group of Fd-3m (spinel structure). The spinel structure serving as a natural mineral structure has excellent structural stability, can maintain good stability under high potential, successfully realizes that the oxidation potential of the material is increased to 4.4V or even more than 4.5V, effectively solves the problems of unstable chemistry and electrochemistry of a solid electrolyte material in an all-solid-state secondary battery and the like, and ensures higher capacity exertion of an anode active material and higher energy density of the whole battery.

In one embodiment, a of the present invention may also be selected from 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3 or 4.4.

In one embodiment, x of the present invention can also be selected to be 0.2, 0.3, 0.5, 0.6, 0.7, or 0.8.

In one embodiment, the solid state electrolyte material has the chemical formula Li_aIn_1-xM_1.5xCl_a+3M is selected from Cu, Zn, Cd, Mg or Ca, a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9.

In one embodiment, the solid state electrolyte material has the chemical formula Li_aSc_1-xM_1.5xCl_a+3M is selected from Cu, Zn, Cd, Mg or Ca, a is more than or equal to 1.5 and less than or equal to 4.5, and x is more than or equal to 0.1 and less than or equal to 0.9.

Preferably, the M is selected from at least one of Mg, Cu and Zn;

and/or a is more than or equal to 2 and less than or equal to 4, and x is more than or equal to 0.1 and less than or equal to 0.6.

Preferably, the solid electrolyte material is a glass-ceramic phase or a crystalline phase.

The solid electrolyte material obtained by the invention can be a glass-ceramic phase or a crystalline phase.

Preferably, the crystal structure of the solid electrolyte material is a spinel structure.

Preferably, the solid electrolyte material is prepared from raw materials including a precursor of lithium, a precursor of a, and a precursor of M.

Preferably, the lithium precursor comprises lithium chloride.

Preferably, the precursor of a comprises the chloride corresponding to a.

The precursor of A is selected from InCl₃(indium trichloride) and/or ScCl₃(scandium chloride).

Preferably, the precursor of M comprises the chloride corresponding to M.

The precursor of M is selected from CuCl₂(copper chloride), ZnCl₂(Zinc chloride), CdCl₂(cadmium chloride), MgCl₂(magnesium chloride) and CaCl₂(calcium chloride).

Preferably, the mass ratio of the lithium chloride to the chloride corresponding to A to the chloride corresponding to M is 1 (1.785-13.044) to (0.056-0.965).

According to another aspect of the present invention, the present invention also relates to a method for producing the solid electrolyte material as described above, comprising the steps of:

and calcining the mixture of the lithium precursor, the precursor of A and the precursor of M under the condition of inert gas.

The synthesis method of the electrolyte is a solid-phase sintering method. Mixing the required raw materials, and performing solid-phase sintering to prepare the corresponding compound. Mixing means include manual mixing or mechanical mixing.

The inert gas of the present invention includes at least one of argon, neon or helium.

Preferably, the calcining comprises: and heating the temperature from room temperature to 300-600 ℃, preserving the heat at the temperature of 300-600 ℃, and then cooling the preserved heat to room temperature.

The method has mild reaction conditions, can avoid using a high-energy ball milling mode, and simplifies the process flow.

In one embodiment, the temperature for the incubation can be selected from 310 deg.C, 320 deg.C, 330 deg.C, 340 deg.C, 350 deg.C, 360 deg.C, 370 deg.C, 380 deg.C, 390 deg.C, 400 deg.C, 410 deg.C, 420 deg.C, 430 deg.C, 440 deg.C, 450 deg.C, 460 deg.C, 470 deg.C, 480 deg.C, 490 deg.C, 500 deg.C, 510 deg.C, 520 deg.C, 530 deg.C, 540 deg.C, 550 deg.C, 560 deg.C, 570 deg.C, 580 deg.C or 590 deg.C.

Preferably, the heating rate of the temperature rising to 300-600 ℃ is 1.8-2.2 ℃/min.

In one embodiment, the heating rate can also be selected to be 1.9 deg.C/min, 2 deg.C/min, or 2.1 deg.C/min.

Preferably, the heat preservation time is 1-40 h.

In one embodiment, the time for the heat preservation can be selected from 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, 31h, 32h, 33h, 34h, 35h, 36h, 37h, 38h or 39 h.

Preferably, the cooling rate of the temperature to the room temperature is 1.8-2.2 ℃/min.

In one embodiment, the cooling rate can also be selected to be 1.9 deg.C/min, 2 deg.C/min, or 2.1 deg.C/min.

Preferably, the calcining further comprises: the mixture is subjected to a first grinding and then to a tabletting.

Preferably, the first grinding time is 25-35 min.

In one embodiment, the first grinding time is 25-35 min, and can be selected from 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min and 34 min.

Preferably, the calcined mixture is subjected to a second grinding.

Preferably, the time of the second grinding is 25-35 min.

In one embodiment, the second grinding time is 25-35 min, and can be selected from 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min and 34 min.

According to another aspect of the present invention, the present invention also relates to a lithium secondary battery comprising the solid electrolyte material as described above.

According to the invention, doping elements are introduced into the electrolyte for component regulation, so that the electrolyte material with a spinel structure is obtained under mild synthesis conditions, the oxidation potential of the material is improved, the electrochemical stability and chemical stability of the positive electrode side are improved, the initial capacity exertion and the cycling stability of the battery are obviously improved, and the application possibility of the solid-state battery is improved.

Preferably, the lithium secondary battery includes a positive electrode, a negative electrode, and an electrolyte layer;

at least one of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material.

The solid electrolyte material in the invention can be used as an additive to be added into a positive electrode material or a negative electrode material. Or as an electrolyte layer for a secondary battery.

The present invention will be further explained with reference to specific examples and comparative examples.

Fig. 1 is an XRD pattern of the solid electrolyte material in example 1.

Fig. 2 is an XRD pattern of the solid electrolyte material in comparative example 1.

Example 1

A solid electrolyte material having a chemical formula of Li₃Sc_0.8Zn_0.3Cl₆。

The preparation method of the solid electrolyte material comprises the following steps:

under the protection of argon atmosphere, 2.199 g LiCl and 0.707 g ZnCl are weighed₂2.093 g of ScCl₃(ii) a Grinding the raw materials with an agate mortar for 30min under the protection of argon atmosphere, pressing the uniformly ground materials into 10 mm-sized pieces by using a tabletting machine, placing the pieces into a single-end quartz tube, sealing the tube in a vacuum tube sealing mode, placing the tube in a muffle furnace for high-temperature sintering, slowly heating the temperature from room temperature to 520 ℃, heating at a rate of 2 ℃/min, preserving the heat for 10h, cooling the tube to room temperature at a rate of 2 ℃/min, placing the tube into a glove box for opening after cooling, and grinding the synthetic materials with the agate mortar for more than 30min to obtain the glass-ceramic phase Li₃Sc_0.8Zn_0.3Cl₆A solid electrolyte powder material.

Example 2

A solid electrolyte material having a chemical formula of Li_2.9Sc_0.7Mg_0.45Cl_5.9。

The preparation method of the solid electrolyte material comprises the following raw materials: 2.262 g LiCl, 1.949 g ScCl₃0.788 g of MgCl₂The other conditions were the same as in example 1.

Example 3

A solid electrolyte material having a chemical formula of Li_3.3In_0.5Cu_0.75Cl_6.3。

The above-mentioned method for producing a solid electrolyte material,the raw materials are removed as follows: 1.991 g LiCl, 1.573 g InCl₃1.435 g of CuCl₂The other conditions were the same as in example 1.

Example 4

A solid electrolyte material having a chemical formula of Li_3.1In_0.4Zn_0.9Cl_6.1。

The preparation method of the solid electrolyte material comprises the following raw materials: 1.918 g LiCl, 1.291 g InCl₃1.791 g ZnCl₂The other conditions were the same as in example 1.

Example 5

A solid electrolyte material having a chemical formula of Li_2.8Sc_0.6Cd_0.6Cl_5.8。

The preparation method of the solid electrolyte material comprises the following raw materials: 1.858 g LiCl, 1.421 g ScCl₃1.721 g of CdCl₂The other conditions were the same as in example 1.

Example 6

A solid electrolyte material having a chemical formula of Li₃In_0.6Ca_0.6Cl_6.3。

The preparation method of the solid electrolyte material comprises the following raw materials: 1.948 g LiCl, 2.033 g InCl₃1.020 g of CaCl₂The other conditions were the same as in example 1.

Example 7

A solid electrolyte material having a chemical formula of Li_3.2Sc_0.1Zn_1.35Cl_6.2。

The preparation method of the solid electrolyte material comprises the following raw materials: 2.026 g LiCl, 0.226 g ScCl₃2.748 g ZnCl₂The other conditions were the same as in example 1.

Example 8

A solid electrolyte material having a chemical formula of Li_2.7Sc_0.9Zn_0.15Cl_5.7。

The preparation method of the solid electrolyte material comprises the following raw materials: 2.111 g LiCl, 2.512 g ScCl₃0.377 g ZnCl₂The other conditions were the same as in example 1.

Example 9

A solid electrolyte material having a chemical formula of Li_1.5Sc_0.7Zn_0.45Cl_4.5。

The preparation method of the solid electrolyte material comprises the following raw materials: 1.377 g LiCl, 2.294 g ScCl₃1.329 g ZnCl₂The other conditions were the same as in example 1.

Example 10

A solid electrolyte material having a chemical formula of Li_4.5In_0.6Cu_0.6Cl_7.5。

The preparation method of the solid electrolyte material comprises the following raw materials: 2.360 g LiCl, 1.642 g InCl₃0.998 g of CuCl₂The other conditions were the same as in example 1.

Comparative example 1

A solid electrolyte material having a chemical formula of Li₃ScCl₆。

Examples of the experiments

Oxidation potential test

Li in example 1₃Sc_0.8Zn_0.3Cl₆And (3) voltage window testing: mixing Li₃Sc_0.8Zn_0.3Cl₆And conductive carbon powder are weighed according to the weight ratio of 70:30, and are uniformly ground by an agate mortar; in an insulating outer cylinder having a diameter of 10mm, the amount of Li is 20mg₃Sc_0.8Zn_0.3Cl₆Conductive carbon powder mixture, 20mg of Li₃Sc_0.8Zn_0.3Cl₆20mg of Li₆PS₅Stacking Cl; the mixture is pressed and molded under the pressure of 360 MPa; then, in Li₆PS₅Laminating a lithium foil on the Cl side, performing pressure molding on the lithium foil at the pressure of 100MPa, arranging stainless steel current collectors above and below the laminated body, attaching current collecting leads to the current collectors, and performing linear sweep voltammetry, wherein the sweep range is 2-5V, and the sweep rate is 0.1 mV/S; by making a tangent to the oxidation peak of the test curve, the point of intersection with the abscissa is the oxidation potential of the material.

The voltage window test method for the solid electrolyte materials of examples 2 to 10 and comparative example is the same as that for Li in example 1 described above₃Sc_0.8Zn_0.3Cl₆Voltage window tests, only the difference of the solid state electrolyte materials.

The results of the oxidation potential test are shown in table 1.

TABLE 1 Oxidation potential test results

Examples and comparative examples	Oxidation potential (V)
		Example 1	4.51
Example 2	4.54
		Example 3	4.52
Example 4	4.47
		Example 5	4.38
Example 6	4.39
		Example 7	4.30
Example 8	4.32
		Example 9	4.31
Example 10	4.35
		Comparative example 1	4.21

Second, testing the cycle performance

In an argon glove box, Li₃Sc_0.8Zn_0.3Cl₆And a positive electrode active material Li (Ni)_0.8Co_0.1Mn_0.1)O₂(i.e., NCM811) was weighed at a weight ratio of 20: 80; grinding the materials uniformly by using an agate mortar to prepare a composite anode material; in an insulating outer cylinder having a diameter of 10mm, 14mg of the above-mentioned positive electrode material and 70mg of the solid electrolyte material Li were used₆PS₅Stacking Cl; pressure molding the mixture at a pressure of 360MPa to obtain a positive electrode and a solid electrolyte layer; next, laminating one aluminum foil on the positive electrode side to form a current collector on the positive electrode side; then, on the opposite side of the solid electrolyte layer from the side in contact with the positive electrode, indium pieces having a thickness and a diameter of 200 μm and 10mm, respectively, were placed as a negative electrode material; press-molding the mixture at a pressure of 80MPa to produce a laminate composed of a positive electrode, a solid electrolyte layer and a negative electrode; next, stainless steel current collectors were disposed on the upper and lower sides of the laminate, and current collecting leads were attached to the current collectors. And (3) carrying out cycle performance test on the assembled solid-state battery under the following test conditions: the current density is 0.3C, and the voltage range is 2.7-4.5V (Li)⁺/Li)。

The solid electrolyte materials of examples 2 to 10 and comparative example 1 were subjected to cycle performance tests according to the methods described above, respectively.

The results of the above cycle performance test are shown in table 2.

TABLE 2 results of the cycle performance test

As can be seen from tables 1 and 2, the present invention obtains an electrolyte material having a spinel structure under mild synthesis conditions by introducing doping elements into the electrolyte and performing component control, thereby achieving an increase in oxidation potential of the material and improving electrochemical stability and chemical stability of the positive electrode side, thereby significantly improving initial capacity exertion and cycling stability of the battery and improving application possibility of the solid-state battery.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.