CN115411353A - Aluminosilicate lithium ion solid electrolyte and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of solid electrolytes, and discloses an aluminosilicate lithium ion solid electrolyte and a preparation method thereof _1‑x Al _1‑x Si _2+x O ₆ (ii) a Wherein x =0.5,0.25, -0.5, -0.75, or-1.00. Because the invention adjusts LiAlSi ₂ O ₆ The ratio of Al to Si predicts Li _1‑x Al _1‑x Si _{2+ x} O ₆ Material system, compare with original LiAlSi ₂ O ₆ Li provided by the invention _1‑x Al _1‑x Si _2+x O ₆ The (x ≠ 0) system possesses better lithium ion conductivity at room temperature. The invention changes LiAlSi ₂ O ₆ Middle Al and SThe electrochemical stability of a series of materials obtained by the ratio of i still keeps a better level, and the safety performance of the materials as a solid electrolyte is guaranteed. In the material, the same group elements are substituted for one or two of Al and Si, so that the conductivity can be further improved.

Description

A kind of aluminosilicate lithium ion solid state electrolyte and preparation method thereof

technical field

The invention belongs to the technical field of solid electrolytes, in particular to an aluminosilicate lithium ion solid electrolyte and a preparation method thereof.

Background technique

At present, with the gradual popularization of new energy electric vehicles and the continuous development of portable electronic devices, people's requirements for the performance and safety of lithium-ion batteries are also increasing. Traditional lithium-ion batteries are representative of commercial secondary batteries. The organic liquid electrolytes used in them have potential safety hazards of leakage, spontaneous combustion, and even explosion, which is an important factor restricting the development of the new energy industry. As an important part of lithium-ion batteries, the electrolyte directly affects the properties of the battery such as capacity, internal resistance, rate charge and discharge performance, operating temperature range, cycle life, and safety performance. An electrolyte with excellent performance can greatly improve the overall performance of lithium batteries. In recent years, all-solid-state batteries based on solid-state electrolytes have attracted much attention. It can use lithium metal as an anode. In addition, solid-state electrolytes avoid the use of diaphragms and organic electrolytes, which greatly improves the energy density and safety of secondary batteries. It is regarded as an important development direction of the new generation of energy storage system.

As an extremely important part of all-solid-state batteries, solid-state electrolytes are currently divided into three categories: polymer electrolytes, sulfide electrolytes, and oxide electrolytes. Polymer solid-state electrolytes are mainly composed of polymer substrates and lithium salts, among which polyethylene oxide (PEO) and its derivatives-based polymer solid-state electrolytes are representative, but their conductivity at room temperature is still low, making them Barriers to large-scale commercialization. Sulfide-based solid-state electrolytes also have high lithium-ion conductivity at room temperature, and they have good mechanical formability, which is very suitable for processing into full batteries, but sulfide materials are prone to react with moisture in the air to generate harmful H ₂ S gas, poor electrochemical stability has become the biggest obstacle to its wide application in the production of safe all-solid-state batteries. Oxide-based solid-state electrolytes have many advantages, including low sensitivity to moisture in the air, high energy density, and good electrochemical stability, but their low Li-ion conductivity at room temperature hinders their widespread application. Therefore, the study of solid-state electrolytes with excellent room temperature Li-ion conductivity and excellent stability is of great significance for the development of all-solid-state batteries.

In recent years, the lithium aluminosilicate material system is considered to be a lithium ion conductor, which is expected to be applied as a solid electrolyte. According to reports, spodumene (β-LiAlSi ₂ O ₆ ) exhibits the advantages of isotropic lithium-ion conductivity, excellent thermal and mechanical stability, and so on. However, β-spodumene exhibits relatively low room temperature Li-ion conductivity (less than 10 ^-10 S/cm) and high Li-ion diffusion barrier (about 0.8eV), which is not very good as a solid-state electrolyte. ideal.

Through the above analysis, the problems and defects in the prior art are:

(1) Existing polymer solid electrolytes and oxide solid electrolytes have low conductivity at room temperature.

(2) The sulfide material of the existing sulfide-based solid-state electrolyte easily reacts with moisture in the air to generate harmful H ₂ S gas, and has poor electrochemical stability.

(3) β-LiAlSi ₂ O ₆ material has excellent electrochemical stability and thermal stability, but its relatively low lithium ion conductivity limits its further application.

Contents of the invention

Aiming at the problems existing in the prior art, the invention provides an aluminosilicate lithium ion solid electrolyte and a preparation method thereof.

The present invention is achieved in this way, a lithium aluminosilicate solid electrolyte, the lithium aluminosilicate solid electrolyte is spodumene and its derivative system, the chemical formula is: Li _1-x Al _1-x Si _{2+ x} O ₆ ; wherein, the value range of x is -1.00～0.5 and x≠0.

Further, if x takes a value of -1.00, then the aluminosilicate lithium ion solid electrolyte is Li ₂ Al ₂ SiO ₆ .

Further, if x takes a value of -0.75, the aluminosilicate lithium ion solid electrolyte is Li _1.75 Al _1.75 Si _1.25 O ₆ .

Further, if x takes a value of -0.5, the aluminosilicate lithium ion solid electrolyte is Li _1.5 Al _1.5 Si _1.5 O ₆ .

Further, if x takes a value of -0.25, the aluminosilicate lithium ion solid electrolyte is Li _1.25 Al _1.25 Si _1.75 O ₆ .

Further, when x is set to be 0.25, the aluminosilicate lithium ion solid electrolyte is Li _0.75 Al _0.75 Si _2.25 O ₆ .

Further, when x is set to be 0.5, the aluminosilicate lithium ion solid electrolyte is Li _0.5 Al _0.5 Si _2.5 O ₆ .

Further, replace Al or Si with the same group elements, Al can be replaced by B or Ga or In or Ta, Si can be replaced by C or Ge or Sn or Pb, then the solid electrolyte Li _1-x A _1-x B _2+x can be obtained O ₆ , A=B, Al, Ga, In, Ta; B=C, Si, Ge, Sn, Pb.

Another object of the present invention is to provide a solid electrolyte for a primary lithium ion battery, which is made of the aluminosilicate lithium ion solid electrolyte.

Another object of the present invention is to provide a secondary lithium ion battery solid electrolyte, which is made of the aluminosilicate lithium ion solid electrolyte.

Another object of the present invention is to provide a method for preparing the aluminosilicate lithium ion solid electrolyte, the preparation method of the aluminosilicate lithium ion solid electrolyte includes: Al and Si in the original LiAlSi ₂ O ₆ The element content is replaced, and the ratio of Al to Si element content is determined. The obtained aluminosilicate lithium ion solid electrolyte is Li _1-x Al _1-x Si _2+x O ₆ , x=0.5, 0.25, -0.25, -0.5, -0.75, or -1.00.

Combining the above-mentioned technical solutions and technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected by the present invention from the following aspects:

First, in view of the technical problems existing in the above-mentioned prior art and the difficulty of solving the problems, closely combine the technical solution to be protected in the present invention and the results and data in the research and development process, etc., to analyze in detail and profoundly how to solve the technical solution of the present invention Technical problems, some creative technical effects brought about after solving the problems. The specific description is as follows:

Based on the first principle and ab initio molecular dynamics, the present invention analyzes the influence of different content ratios of Al element and Si element in the β-LiAlSi ₂ O ₆ material on its lithium ion conductivity. In the field of energy, the invention can be used as a solid electrolyte for lithium ion batteries, and the batteries include primary batteries and secondary batteries.

The purpose of the present invention is to improve the conductivity of lithium ions by adjusting the content ratio of Al/Si element in the β-LiAlSi ₂ O ₆ material. In order to analyze the optimal ratio of Al/Si element content, the present invention replaces Al and Si elements in the original β-LiAlSi ₂ O ₆ , thereby constructing a material system, that is, Li _1-x Al _{1- x} Si _{2 +x} O ₆ (x=0.5, 0.25, 0, -0.25, -0.5, -0.75, -1.00). The present invention adopts an ab initio molecular dynamics simulation calculation method based on density functional theory to analyze the conductivity of lithium ions in Li _1-x Al _1-x Si _2+x O ₆ .

As can be seen from the experimental results, the Li _1-x Al _1-x Si _2+x O ₆ unit cell provided by the present invention generally has a larger band gap (greater than 3.5eV), indicating that its structure has good electrochemical stability and is applicable to The solid electrolyte can effectively inhibit the shuttle of electrons in it and avoid the self-discharge process of the battery. During the ab initio molecular dynamics simulation of the Li _1-x Al _1-x Si _2+x O ₆ material system at high temperature, the crystal structure framework remains intact, indicating its good thermal stability. The value of x in Li _1-x Al _1-x Si _2+x O ₆ is negative, that is, the ratio of Al to Si increases, and when the unit cell is transformed into a lithium-rich structure, the conductivity at room temperature is several orders of magnitude higher than that of the original structure Among them, Li ₂ Al ₂ SiO ₆ has the lowest lithium ion migration barrier and the most excellent electrical conductivity.

Second, regarding the technical solution as a whole or from the perspective of a product, the technical effects and advantages of the technical solution to be protected by the present invention are specifically described as follows:

(1) Since the ratio of Al to Si in LiAlSi ₂ O ₆ is adjusted, Li _1-x Al _1-x Si _2+x O ₆ (x=0.5, 0.25, 0, -0.25, -0.5, -0.75 or -1.00) material system, compared with the original LiAlSi ₂ O ₆ , the Li _1-x Al _1-x Si _2+x O ₆ (x≠0) system has better lithium ion conductivity at room temperature.

(2) A series of materials obtained by changing the ratio of Al to Si in LiAlSi ₂ O ₆ still maintain a good electrochemical stability, and the safety performance as a solid electrolyte is guaranteed.

(3) Compared with the original spodumene LiAlSi ₂ O ₆ , when the value of Al/Si is increased (that is, when x is less than 0 in Li _1-x Al _1-x Si _2+x O ₆ ), the lithium ion The migration barrier will be significantly reduced. Among them, the lithium ion migration barrier of Li ₂ Al ₂ SiO ₆ is reduced by about 40%, which is a significant drop, and the lithium ion conductivity at room temperature is also significantly improved.

Third, as an auxiliary evidence of the inventiveness of the claims of the present invention, it is also reflected in the expected benefits and commercial value after the transformation of the technical solution of the present invention:

The invention provides a design method of a silicate solid electrolyte, which has high lithium ion conductivity and cheap raw materials, and can greatly reduce the manufacturing cost of the solid electrolyte.

Description of drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings that need to be used in the embodiments of the present invention. Obviously, the drawings described below are only some embodiments of the present invention. For Those of ordinary skill in the art can also obtain other drawings based on these drawings without making creative efforts.

Fig. 1 is the flow chart of the design method of the aluminosilicate lithium ion solid electrolyte provided by the embodiment of the present invention;

Figure 2 is a crystal structure diagram of the Li _1-x Al _1-x Si _2+x O ₆ (x=0.5,0.25,0,-0.25,-0.5,-0.75,-1.00) material system provided by the embodiment of the present invention ;

Figure 3 is a diagram of the total electron density of states of the Li _0.5 Al _0.5 Si _2.5 O ₆ material provided by the embodiment of the present invention;

Figure 4 is a diagram of the total electron density of states of the Li _0.75 Al _0.75 Si _2.25 O ₆ material provided by the embodiment of the present invention;

Fig. 5 is a diagram of the total electron density of states of the LiAlSi ₂ O ₆ material provided by the embodiment of the present invention;

Figure 6 is a diagram of the total electron density of states of the Li _1.25 Al _1.25 Si _1.75 O ₆ material provided by the embodiment of the present invention;

Figure 7 is a diagram of the total electron density of states of the Li _1.5 Al _1.5 Si _1.5 O ₆ material provided by the embodiment of the present invention;

Fig. 8 is a diagram of the total electronic density of states of the Li _1.75 Al _1.75 Si _1.25 O ₆ material provided by the embodiment of the present invention;

Fig. 9 is a diagram of the total electronic density of states of the Li ₂ Al ₂ SiO ₆ material provided by the embodiment of the present invention;

Fig. 10 is an average mean square displacement diagram of lithium ions at different temperatures for the Li ₂ Al ₂ SiO ₆ material provided by the embodiment of the present invention;

Figure 11 shows the electrical conductivity of the Li _1-x Al _1-x Si _2+x O ₆ (x=0.5, 0.25, 0, -0.25, -0.5, -0.75, -1.00) material system provided by the embodiment of the present invention with temperature change map;

Figure 12 is the lithium ion migration of the Li _1-x Al _1-x Si _2+x O ₆ (x=0.5,0.25,0,-0.25,-0.5,-0.75,-1.00) material system provided by the embodiment of the present invention The trend graph of the potential barrier and the conductivity with the x value at room temperature;

Fig. 13 is Li _1-x Al _1-x Si _2+x O ₆ (x=0.5,0.25,0,-0.25,-0.5,-0.75,-1.00) material system provided by the embodiment of the present invention Lithium ion diffusion Trend chart of channel size versus x value.

Figure 14 is Li _1-x Al _1-x (Si _1-y Ge _y ) _2+x O ₆ (x=0.5,0.25,0,-0.25,-0.5,-0.75,-1.00) provided by the embodiment of the present invention ,0≤y≤1) The electrical conductivity of the material system varies with temperature and the lithium ion migration barrier and the electrical conductivity at room temperature vary with the y value;

Detailed ways

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

Aiming at the problems existing in the prior art, the present invention provides an aluminosilicate lithium ion solid state electrolyte and a design method thereof. The present invention will be described in detail below with reference to the accompanying drawings.

1. Explain the embodiment. In order to make those skilled in the art fully understand how to implement the present invention, this part is an explanatory embodiment for explaining the technical solution of the claims.

The aluminosilicate lithium-ion solid electrolyte provided in the embodiment of the present invention is spodumene and its derivative system, and its chemical formula is: Li _1-x Al _1-x Si _2+x O ₆ ; where x=0.5, 0.25, -0.25 , -0.5, -0.75, or -1.00.

The optimal proportion of the solid electrolyte provided by the embodiment of the present invention includes the following components:

Li _0.5 Al _0.5 Si _2.5 O ₆ ;

Li _0.75 Al _0.75 Si _2.25 O ₆ ;

Li _1.25 Al _1.25 Si _1.75 O ₆ ;

Li _1.5 Al _1.5 Si _1.5 O ₆ ;

Li _1.75 Al _1.75 Si _1.25 O ₆ ;

Li ₂ Al ₂ SiO ₆ .

The embodiment of the present invention also provides a preparation method of aluminosilicate lithium ion solid electrolyte, including: by replacing the Al and Si elements in the original β-LiAlSi ₂ O ₆ to construct a material system, and determine the Al/Si The optimal ratio of element content: Li _1-x Al _1-x Si _2+x O ₆ , x=0.5, 0.25, 0, -0.25, -0.5, -0.75 or -1.00; Ab initio molecular dynamics simulation calculation method to analyze the conductivity of lithium ions in Li _1-x Al _1-x Si _2+x O ₆ .

Example 1

In the embodiment of the present invention, the conductivity of lithium ions is improved by adjusting the content ratio of Al/Si element in the β-LiAlSi ₂ O ₆ material. In order to analyze the optimal ratio of Al/Si element content, the present invention replaces Al and Si elements in the original β-LiAlSi ₂ O ₆ , thereby constructing a material system, that is, Li _1-x Al _{1- x} Si _{2 +x} O ₆ (x=0.5, 0.25, 0, -0.25, -0.5, -0.75, -1.00). The conductivity of lithium ions in Li _{1- x} Al _1-x Si _2+x O ₆ was analyzed by ab initio molecular dynamics simulation calculation method based on density functional theory.

(1) As shown in Figure 1, the purpose of the present invention provided by the embodiment of the present invention is to provide Li _1-x Al _1-x Si _2+x O _The optimal ratio of elements, the design method includes the following steps:

S101, establish Li _1-x Al _1-x Si _2+x O ₆ models with different Al/Si element contents, and optimize the structures of the constructed models respectively, and the lattice parameters and ion positions are completely relaxed;

S102, based on structural optimization, calculate the electronic density of state of the constructed unit cell model, and analyze the electrochemical stability of Li _1-x Al _1-x Si _2+x O ₆ as a solid electrolyte through the band gap size;

S103, calculate the electrical conductivity properties of the material according to the Nernst-Einstein equation, and use the Zeo++ program to measure the lithium ion diffusion channel of the Li _1-x Al _1-x Si _2+x O ₆ system.

优化后的Li_{1- x}Al_1-xSi_2+xO₆晶体结构如图2所示。(2) In step S101 provided by the embodiment of the present invention, structural optimization is performed on the constructed model, and the lattice parameters and ion positions are completely relaxed until the total energy and ion force are respectively less than 10 ^-5 eV and

The optimized crystal structure of Li _{1- x} Al _1-x Si _2+x O ₆ is shown in Fig. 2 .

(3) In step S102 provided by the embodiment of the present invention, in order to analyze the electrochemical stability of Li _1-x Al _1-x Si _2+x O ₆ as a solid electrolyte, on the basis of its structural optimization, the The constructed unit cell model was used to calculate the electronic density of states, so as to analyze the electrochemical stability from the perspective of the electronic structure of the material. As shown in Figures 3-9, the band gap of undoped LiAlSi ₂ O ₆ is about 4.5eV, and the higher band gap indicates that it has very good electrochemical stability. For Li _1-x Al _{1- x} Si _2+x O ₆ , it can be divided into two cases. When x is greater than 0, that is, the lithium-poor state, as x increases, the band gap tends to decrease. When x is less than 0, that is, the lithium-rich state, the band gap also decreases with the decrease of x value. _However , the band gaps of all materials are greater than 3.5eV, indicating that Li _1-x Al _{1 -x} Si _2+x O ₆ (x=0.5,0.25,0,-0.25 ,-0.5,-0.75,-1.00) materials have good electrochemical stability.

(4) In step S103 provided by the embodiment of the present invention, the lithium ion conductivity property of the material is calculated according to the following Nernst-Einstein equation:

其中MSD为锂离子扩散的平均均方位移，可由从头算分子动力学模拟计算得到；平均均方位移值与时间的比值越大，说明锂离子的扩散系数越大，相应的锂离子电导率越大。Among them, σ is the electrical conductivity, n is the number density of lithium ions, e is the charged amount of the elementary charge, Z is the valence state of a single lithium ion, k _B is the Boltzmann constant, T is the temperature, and D is the temperature of the lithium ion. Diffusion coefficient. The physical quantities except the diffusion coefficient D can be obtained from the unit cell parameters and calculation simulation parameters, the diffusion coefficient

Among them, MSD is the average mean square displacement of lithium ion diffusion, which can be calculated by ab initio molecular dynamics simulation; the larger the ratio of the average mean square displacement value to time, the larger the diffusion coefficient of lithium ions is, and the higher the corresponding lithium ion conductivity is. big.

(5) Figure 10 shows the average mean square displacement of lithium ions at different temperatures as a function of time when x in Li _1-x Al _1-x Si _2+x O ₆ is -1 (ie Li ₂ Al ₂ SiO ₆ ) The results show that the higher the temperature, the larger the ratio of the average mean square displacement to time, that is, the larger the diffusion coefficient of lithium ions, indicating that the conductivity of lithium ions is affected by temperature, and the higher the temperature, the greater the conductivity of lithium ions.

两边取对数并变形得

其中

作图

由图的斜率计算得到锂离子迁移势垒E_a的值，其中斜率越小，迁移势垒越大；将模拟温度设置为1073K～2273K，温度间隔为200K；由多个温度点的数据作图，由斜率的大小推导得知迁移势垒的大小。迁移势垒是锂离子迁移所需的能量大小，迁移势垒越大，说明锂离子的迁移越困难，相应地锂离子电导率则较低。锂离子的迁移势垒越小代表锂离子的电导率性质越优异。(6) For the Nernst-Einstein equation

Take the logarithm on both sides and transform to

in

drawing

Calculate the value of the lithium ion migration barrier E _a from the slope of the graph, where the smaller the slope, the larger the migration barrier; set the simulation temperature to 1073K ~ 2273K, and the temperature interval is 200K; plot the data from multiple temperature points , the size of the migration barrier can be deduced from the size of the slope. The migration barrier is the amount of energy required for the migration of lithium ions. The larger the migration barrier is, the more difficult it is for lithium ions to migrate, and accordingly the conductivity of lithium ions is lower. The smaller the migration barrier of lithium ions, the better the conductivity of lithium ions.

(7) Ion conductivity is the key factor determining the internal resistance and rate performance of the battery. To determine the conductivity of lithium ions in the temperature range of 1073K to 2273K in the Li _1-x Al _1-x Si _2+x O ₆ material system, it is determined by The data at high temperature are linearly extrapolated to the conductivity of lithium ions at room temperature of 300K; the original LiAlSi ₂ O ₆ calculated lithium ion conductivity at room temperature is the lowest, when x is positive, the lithium ion conductivity at room temperature increases; when x is When the value is negative, the lithium ion concentration of the material increases, and the lithium ion conductivity at room temperature increases significantly; among them, Li ₂ Al ₂ SiO ₆ has the best lithium ion conductivity at room temperature.

₍ 8) Figure 12 summarizes the lithium _ion migration barrier and _{room temperature} The variation trend of lithium ion conductivity with x value. The lithium ion migration barrier is the highest in the original LiAlSi ₂ O ₆ , and when x is positive (that is, the Si/Al ratio increases), the migration barrier decreases as the Si/Al ratio increases. When x is a negative value (that is, the Al/Si ratio increases), the migration barrier decreases with the increase of the Al/Si ratio, and the minimum value appears at x=-1.0, indicating that lithium in Li ₂ Al ₂ SiO ₆ The ion diffusion needs to overcome the lowest barrier, and lithium ions are more likely to migrate in the material, so the lithium ion conductivity of the material is the best.

(9) The size of the lithium ion transport channel also affects the conductivity of lithium ions. Figure 13 shows the Li _1-x Al _1-x Si _2+x O ₆ (x=0.5,0.25,0,- 0.25, -0.5, -0.75, -1.00) system of lithium ion diffusion channel measurement results. As shown in the figure, compared with the original LiAlSi ₂ O ₆ , Li ₂ Al ₂ SiO ₆ (that is, when x=-1.0), the transmission channel of lithium ions has been significantly improved, which is also because it has a higher lithium ion The reason for the conductivity.

(10) After adopting the above technical scheme, because the ratio of Al to Si in LiAlSi ₂ O ₆ is adjusted, Li _1-x Al _{1- x} Si _2+x O ₆ (x=0.5,0.25,0,-0.25, -0.5 _, -0.75, _-1.00 ) material _{system ,} the present invention _{has better} lithium ionic conductivity.

The electrochemical stability of the series of materials obtained by changing the ratio of Al to Si in LiAlSi ₂ O ₆ in the embodiment of the present invention still maintains a good level, and the safety performance as a solid electrolyte is guaranteed.

Compared with the original spodumene LiAlSi ₂ O ₆ , when the present invention increases the value of Al/Si (ie Li _1-x Al _1-x Si _2+x O ₆ when x is less than 0) the migration of lithium ions The potential barrier will be significantly reduced. Among them, the lithium ion migration barrier of Li ₂ Al ₂ SiO ₆ is reduced by about 40%, which is a significant drop, and the lithium ion conductivity at room temperature is also significantly improved.

Example 2

The embodiment is similar to Example 1, except that the Si element in Li _1-x Al _1-x Si _2+x O ₆ is partially or completely replaced with its congener elements to obtain Li _1-x Al _1-x (Si _1-y Ge _y ) _2+x O ₆ (x=0.5,0.25,0,-0.25,-0.5,-0.75,-1.00,0≤y≤1). As shown in Figure 14, with the increase of Ge content, the conductivity of the electrolyte can be increased by nearly 1 order of magnitude.

The above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Anyone familiar with the technical field within the technical scope disclosed in the present invention, whoever is within the spirit and principles of the present invention Any modifications, equivalent replacements and improvements made within shall fall within the protection scope of the present invention.

Claims (10)

1. The aluminosilicate lithium ion solid electrolyte is characterized by being spodumene and a derivative system, and having a chemical formula as follows: li _1-x Al _1-x Si _2+x O ₆ (ii) a Wherein, the value range of x is-1.00-0.5, and x is not equal to 0.

2. As claimed inThe aluminosilicate lithium ion solid electrolyte of claim 1, wherein x is-1.00, and the aluminosilicate lithium ion solid electrolyte is Li ₂ Al ₂ SiO ₆ 。

3. The aluminosilicate lithium ion solid electrolyte of claim 1, wherein the value of x is-0.75, and the aluminosilicate lithium ion solid electrolyte is Li _1.75 Al _1.75 Si _1.25 O ₆ 。

4. The aluminosilicate lithium ion solid electrolyte of claim 1, wherein x is in a range of-0.5, and wherein the aluminosilicate lithium ion solid electrolyte is Li _1.5 Al _1.5 Si _1.5 O ₆ 。

5. The aluminosilicate lithium ion solid electrolyte of claim 1, wherein x is in a range of-0.25, and wherein the aluminosilicate lithium ion solid electrolyte is Li _1.25 Al _1.25 Si _1.75 O ₆ 。

6. The aluminosilicate lithium ion solid electrolyte of claim 1, wherein the value of x is 0.25, and the aluminosilicate lithium ion solid electrolyte is Li _0.75 Al _0.75 Si _2.25 O ₆ (ii) a x is 0.5, the aluminosilicate lithium ion solid electrolyte is Li _0.5 Al _0.5 Si _2.5 O ₆ 。

7. A primary lithium ion battery solid electrolyte, characterized in that it is made of the aluminosilicate lithium ion solid electrolyte of any one of claims 1 to 7.

8. A solid electrolyte for a secondary lithium ion battery, characterized in that it is produced from the aluminosilicate lithium ion solid electrolyte according to any one of claims 1 to 7.

9. A method for producing the aluminosilicate lithium ion solid electrolyte according to any one of claims 1 to 7, wherein the method for producing the aluminosilicate lithium ion solid electrolyte comprises: for original LiAlSi ₂ O ₆ Replacing Al and Si contents, determining the ratio of Al and Si contents, and obtaining the aluminosilicate lithium ion solid electrolyte of Li _{1- x} Al _1-x Si _2+x O ₆ X =0.5,0.25, -0.5, -0.75, or-1.00.

10. The aluminosilicate lithium ion solid electrolyte according to claim 1, wherein substitution of Al with B, ga, in or Ta, or substitution of Si with C, ge, sn or Pb is performed by substituting Al or Si with a group element to obtain a solid electrolyte Li _1-x A _1-x B _2+x O ₆ ，A＝B,Al,Ga,In,Ta；B＝C,Si,Ge,Sn,Pb。

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