Halide solid electrolyte, and preparation method therefor and use thereof

Abstract

Disclosed are a halide solid electrolyte, and a preparation method therefor and the use thereof. The chemical formula of the halide solid electrolyte is as represented by Li2-xTaxZr1-xCl6, wherein x in the formula is 0.2-0.4. The halide solid electrolyte is simple in terms of preparation process, and has a relatively high ionic conductivity.

Description

Halide solid electrolyte and its preparation method and application Technical Field

[0001] The invention relates to a halide solid electrolyte and a preparation method and application thereof. Background Art

[0002] With the rapid development of the economy and the acceleration of the global industrial process, mankind is facing problems such as the depletion of fossil fuels and increased environmental pollution. However, new energy sources that are widely used in daily life, such as solar energy and wind energy, generally have the problem of time and space mismatch. To solve this problem, electrochemical energy storage batteries with high energy, high power density and high conversion efficiency are highly anticipated. Among them, lithium-ion batteries have been widely used in daily life and production due to their high specific energy and high output power. However, traditional lithium-ion batteries use flammable and explosive organic matter as electrolytes, which are prone to failure. Therefore, there is an urgent need to develop a next-generation battery system with both high specific energy and high safety. The development of all-solid-state lithium-ion batteries can greatly improve battery safety and solve the problem of flammable and explosive electrolytes.

[0003] Solid electrolytes are an important component of all-solid-state lithium-ion batteries. Among the many solid electrolytes, halide solid electrolytes have attracted widespread attention due to their excellent performance. The general formula of halide solid electrolytes can be, for example, Li3MX6 (M = In, Y, Sc, Er, etc.; X = Cl, Br, etc.). They have high ionic conductivity (10 -4 ~10 -3 S cm -1 ), a wide electrochemical window, and good chemical stability with cathode materials. Notably, due to the low electronegativity of halogen atoms, they possess high oxidative stability, thus exhibiting excellent interfacial stability with 4V-class cathode active materials without the need for any coating. Li2ZrCl6 is a typical representative of halide solid electrolytes.

[0004] Through literature research, we found that the ionic conductivity of Li2ZrCl6 at room temperature is 0.2~0.4×10 -3 mS·cm -1 However, its ionic conductivity is comparable to that of other halide solid electrolytes, such as Li3YBr6 (0.72~1.7×10 -3 mS·cm -1 )、Li3InCl6(0.84~2.04×10 -3 mS·cm -1 ) is still relatively low compared with others (Energy Environ. Sci., 2020, 13, 1429-1461), so a new strategy needs to be developed to further improve the ionic conductivity of Li2ZrCl6.

[0005] Summary of the Invention

[0006] In view of the technical problem that the ionic conductivity of the halide electrolyte in the above-mentioned prior art is still low, the purpose of the present invention is to provide a halide solid electrolyte with simple process and high ionic conductivity and a preparation method thereof.

[0007] Through in-depth research, the inventors found that by doping an appropriate amount of high-valent cation Ta into Li2ZrCl6, anion gaps or cation vacancies can be generated, thereby further improving the ionic conductivity of Li2ZrCl6.

[0008] Specifically, the first aspect of the present invention provides a halide solid electrolyte, the chemical formula of the halide solid electrolyte is as follows: 2-x Ta x Zr 1-x As shown in Cl6, where x is 0.2-0.4.

[0009] In some specific embodiments, x is 0.25-0.3, preferably 0.27-0.29.

[0010] In some specific embodiments, the halide solid electrolyte is prepared by mixing and grinding a lithium source LiCl, a zirconium source ZrCl4, and a tantalum source TaCl5.

[0011] In some embodiments, the grinding is ball milling or sand milling.

[0012] A second aspect of the present invention provides a method for preparing a halide solid electrolyte, the method comprising the following steps:

[0013] (1) lithium source LiCl, zirconium source ZrCl4 and tantalum source TaCl5 are weighed respectively according to the molar ratio of (2-x): (1-x): x, where x is 0.2-0.4;

[0014] (2) mixing the lithium source LiCl, zirconium source ZrCl4 and tantalum source TaCl5 weighed in step (1) and grinding them to obtain a halide solid electrolyte;

[0015] Wherein, in step (2), the grinding speed is 450-700 rpm.

[0016] In some specific embodiments, x is 0.25-0.3, preferably 0.27-0.29.

[0017] In some embodiments, in step (2), the grinding speed is 550-650 rpm; and / or

[0018] The total grinding time is 5-20 hours, preferably 8-15 hours; and / or

[0019] The grinding is performed intermittently, preferably, grinding for 10-15 minutes and pausing for 3-10 minutes.

[0020] In some embodiments, the grinding is ball milling or sand milling.

[0021] In some embodiments, the ball-to-material ratio of the ball mill is 30-50:1, preferably 35-45:1; and / or

[0022] The ball mill uses ball milling beads made of zirconium oxide, and the diameter of the ball milling beads is 3-10 mm.

[0023] In some specific embodiments, both step (1) and step (2) are performed in an inert atmosphere, preferably an argon atmosphere.

[0024] In some embodiments, the preparation method does not include a heat treatment step.

[0025] The third aspect of the present invention provides a halide solid electrolyte prepared by the preparation method of the present invention.

[0026] A fourth aspect of the present invention provides use of the halide solid electrolyte of the present invention in a battery.

[0027] A fifth aspect of the present invention provides a solid electrolyte layer comprising the halide solid electrolyte of the present invention.

[0028] A sixth aspect of the present invention provides a battery comprising a solid electrolyte layer, a positive electrode and a negative electrode, wherein at least one of the solid electrolyte layer, the positive electrode and the negative electrode comprises the halide solid electrolyte of the present invention.

[0029] A seventh aspect of the present invention provides a solid electrolyte battery comprising a solid electrolyte layer, a positive electrode and a negative electrode, wherein the solid electrolyte layer comprises the solid electrolyte of the present invention.

[0030] The halide electrolyte of the present invention has a simple preparation process and has high ion conductivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 shows the XRD patterns of Li2ZrCl6 halide solid electrolytes doped with different proportions of Ta elements. The horizontal axis is the double diffraction angle (2θ), in degrees; the vertical axis is the intensity, without units. 2-x Ta x Zr 1-xAs shown in Cl6, Ta40-LZC represents a halide solid electrolyte with x being 0.40, Ta35-LZC represents a halide solid electrolyte with x being 0.35, Ta30-LZC represents a halide solid electrolyte with x being 0.30, Ta20-LZC represents a halide solid electrolyte with x being 0.20, Ta10-LZC represents a halide solid electrolyte with x being 0.10, and LZC represents a halide solid electrolyte with x being 0.

[0032] Figure 2 shows the ionic conductivity statistics of Li2ZrCl6 halide solid electrolytes doped with different proportions of Ta. The horizontal axis shows the Ta doping amount, i.e., the value of x.

[0033] Figure 3 shows Li 1.72 Ta 0.28 Zr 0.72 Electrochemical performance diagram of Cl6 halide solid electrolyte adapted to high-voltage positive electrode. DETAILED DESCRIPTION

[0034] The present invention will be further described below through specific embodiments. Unless otherwise specified, the technical terms used herein have the same meanings as those generally understood by those skilled in the art.

[0035] Numerical limits or ranges stated herein are inclusive of the endpoints and specifically include all values ​​and subranges within the numerical limits or ranges.

[0036] The first aspect of the present invention provides a halide solid electrolyte, the chemical formula of the halide solid electrolyte is as follows: 2-x Ta x Zr 1-x As shown in Cl6, where x is 0.2-0.4.

[0037] It can be understood that the halide solid electrolyte of the present invention can be in the form of powder or particles composed of the compound of the above-mentioned chemical composition, or it can be in the form of a molded body formed by compressing the powder, a molded body formed by a mixture of powder and a binder, and a coating film formed by applying a coating containing powder, a binder and a solvent and then heating to remove the solvent.

[0038] In some preferred embodiments of the present invention, x is 0.25-0.3, more preferably 0.27-0.29. Specifically, x can be any value selected from 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39 or 0.4, or a range consisting of any two of the above values.

[0039] In some preferred embodiments of the present invention, the halide solid electrolyte is prepared by mixing and grinding a lithium source LiCl, a zirconium source ZrCl4, and a tantalum source TaCl5. Specific conditions can be adopted from the relevant conditions of the preparation method of the second aspect of the present invention.

[0040] A second aspect of the present invention provides a method for preparing a halide solid electrolyte, the method comprising the following steps:

[0041] (1) weighing a lithium source LiCl, a zirconium source ZrCl4, and a tantalum source TaCl5 according to a molar ratio of (2-x): (1-x): x based on lithium, zirconium, and tantalum, respectively, where x is 0.2-0.4;

[0042] (2) mixing the lithium source LiCl, zirconium source ZrCl4 and tantalum source TaCl5 weighed in step (1) and grinding them to obtain a halide solid electrolyte;

[0043] Wherein, in step (2), the grinding speed is 450-700 rpm.

[0044] In the present invention, the grinding process in step (2) can, on the one hand, make the various substances evenly mixed, and at the same time promote the mutual doping of the various substances to generate a new type of halide solid electrolyte.

[0045] In some preferred embodiments of the present invention, x is 0.25-0.3, more preferably 0.27-0.29. Specifically, x can be any value selected from 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39 or 0.4, or a range consisting of any two of the above values.

[0046] According to the preparation method of the present invention, in step (2), the grinding is not particularly limited as long as the halide solid electrolyte of the present invention can be prepared, and for example, it can be carried out by high-energy ball milling. For example, the grinding can be carried out under the following conditions: the rotation speed is preferably 550-650 rpm; the total grinding time can be, for example, 5-20 h, preferably 8-15 h. The grinding method is preferably ball milling or sand milling, wherein the material-to-ball ratio can be 30-50:1, preferably 35-45:1. Furthermore, the ball milling preferably uses ball milling beads made of zirconia, and more preferably, the ball milling beads have a diameter of 3-10 mm. The grinding can be carried out, for example, using a planetary ball mill.

[0047] In addition, grinding is preferably carried out in an intermittent manner to ensure a better preparation effect. Specifically, intermittent grinding can include: grinding for 10-15 minutes, pausing for 3-10 minutes, and repeating until the grinding time is over. The pause time in this process can release heat, avoiding excessive temperature during grinding and damage to the crystal structure; on the other hand, the various substances can be concentrated during this time to avoid problems such as insufficient reaction caused by uneven mixing at the beginning, making grinding smoother and the generated anion-cation dual-doped electrolyte more in line with the requirements.

[0048] In order to prepare the desired halide solid electrolyte, according to the preparation method of the present invention, both step (1) and step (2) are carried out in an inert atmosphere, preferably in an argon atmosphere. Specifically, the weighing and mixing of step (1) can be carried out in a glove box.

[0049] By adopting the above-mentioned preparation method of the present invention, the desired halide electrolyte can be obtained solely by grinding. This preparation method does not include a heat treatment step. The heat treatment herein includes heating, sintering, etc. In other words, no additional heating operation is required during the preparation process. It will be understood that the above-mentioned non-heat treatment step does not exclude the heat generated during the grinding process.

[0050] The third aspect of the present invention provides a halide solid electrolyte prepared by the preparation method described above.

[0051] A fourth aspect of the present invention provides the use of the halide solid electrolyte of the present invention in a battery, preferably a lithium-ion battery.

[0052] A fifth aspect of the present invention provides a solid electrolyte layer, which comprises the halide solid electrolyte of the present invention.

[0053] A sixth aspect of the present invention provides a battery comprising a solid electrolyte layer, a positive electrode and a negative electrode, wherein at least one of the solid electrolyte layer, the positive electrode and the negative electrode comprises the halide solid electrolyte of the present invention.

[0054] A seventh aspect of the present invention provides a solid electrolyte battery, which includes a solid electrolyte layer, a positive electrode and a negative electrode, wherein the solid electrolyte layer contains the solid electrolyte described above in the present invention.

[0055] The solid electrolyte layer of the present invention comprises the halide solid electrolyte of the present invention. Furthermore, the solid electrolyte layer can be sandwiched between a positive electrode and a negative electrode, and external terminals can be connected to the positive and negative electrodes for electrical connection to the outside, thereby forming a battery.

[0056] Furthermore, the battery of the present invention may be a battery in which the pores of the battery main body composed of the positive electrode and the negative electrode are filled with a halide solid electrolyte.

[0057] In the present invention, the battery may be a laminated body comprising a positive electrode, a negative electrode, and a solid electrolyte layer, or a wound body comprising the laminated body. Examples of the battery include laminated batteries, prismatic batteries, cylindrical batteries, coin batteries, and button batteries.

[0058] In the present invention, there is no particular limitation on the type of lithium battery, and it may be, for example, a lithium metal battery, a lithium ion battery, a lithium sulfur battery, or a lithium air battery.

[0059] In the lithium battery of the present invention, the negative electrode may include a negative electrode active material that can release and accept lithium ions. For example, the negative electrode active material may be lithium metal, a lithium alloy, or a carbon material doped or undoped with lithium ions. In some embodiments, the negative electrode active material is a carbon material doped or undoped with lithium ions. Such a carbon material may be graphite or amorphous carbon, and any carbonaceous material such as activated carbon, carbon fiber, carbon black, medium carbon microbeads, etc. may be used.

[0060] In the lithium battery of the present invention, the positive electrode may include a positive electrode active material capable of releasing and accepting lithium ions. In some embodiments, the positive electrode active material may be, for example, a composite oxide or sulfide of lithium and a transition metal, such as MoS2, TiS2, MnO2, V2O5, or the like; or a conductive polymer, such as polyaniline, polypyrrole, or the like. Preferred examples of these composite oxides include LiCoO2, LiMnO2, LiMn2O4, LiNiO2, and the like.

[0061] Such a solid electrolyte battery can be manufactured, for example, by the following method: A halide solid electrolyte powder is placed in a molded battery and compressed. The resulting compressed electrolyte sheet is then sandwiched between two electrodes. For example, stainless steel electrodes and lithium-indium alloy electrodes can be used.

[0062] Example

[0063] The experimental methods in the following examples are conventional methods unless otherwise specified.

[0064] In the following examples and comparative examples, the reagents and instrument models used are as follows:

[0065] LiCl, Aladdin, L433508-100g;

[0066] ZrCl4, Aladdin, Z431132-100g;

[0067] TaCl5, Aladdin, T161496-25g;

[0068] Ball mill, Changsha Tianchuang powder planetary ball mill;

[0069] Ball mill jar, Chishun Technology, zirconia ball mill jar 50mL.

[0070] Comparative Example 1

[0071] This comparative example is used to illustrate the preparation method of a comparative halide solid electrolyte.

[0072] (1) In a glove box filled with Ar gas, lithium source (LiCl) and zirconium source (ZrCl4) were weighed in a molar ratio of 2:1, and then the weighed materials were placed in a ball mill, ball milling beads (ball-to-material mass ratio of 40:1, ball milling beads are made of zirconium oxide, size Ø = 5 mm) were added, and the ball milling jar was sealed in the glove box;

[0073] (2) The lithium source and the zirconium source were ball-milled using the following ball-milling conditions: a rotation speed of 600 rpm, a 15-minute pause, and a total milling time of 10 hours. This yielded the comparative halide solid electrolyte Li2ZrCl6.

[0074] Comparative Example 2

[0075] This comparative example is used to illustrate the preparation method of a comparative halide solid electrolyte.

[0076] (1) In a glove box filled with Ar gas, lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4) were weighed in a molar ratio of 1.9:0.1:0.9, and then the weighed materials were placed in a ball mill, and ball milling beads (ball-to-material mass ratio was 40:1, ball milling beads were made of zirconium oxide, and the size was Ø = 5 mm) were added and the ball mill was sealed in the glove box;

[0077] (2) The lithium source and zirconium source were ball milled under the following ball milling conditions: the rotation speed was 600 rpm, the rotation time was 15 minutes, the rest time was 5 minutes, and the ball milling time was reversed and opened for a total of 10 hours. 1.9 Ta 0.1 Zr 0.9 Cl6.

[0078] Example 1

[0079] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0080] (1) In a glove box filled with Ar gas, lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4) were weighed in a molar ratio of 1.8:0.2:0.8, and then the weighed materials were placed in a ball mill, and ball milling beads (ball-to-material mass ratio of 40:1, ball milling beads are made of zirconium oxide, size Ø = 5 mm) were added and the ball mill was sealed in the glove box;

[0081] (2) The lithium source and zirconium source were ball milled under the following ball milling conditions: the rotation speed was 600 rpm, the rotation time was 15 minutes, the rest time was 5 minutes, and the ball milling time was reversed and opened for a total of 10 hours. 1.8 Ta 0.2 Zr 0.8 Cl6.

[0082] Example 2

[0083] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0084] In addition to changing the molar ratio of lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4), the halide solid electrolyte Li 1.7 Ta 0.3 Zr 0.7 Cl6.

[0085] Example 3

[0086] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0087] In addition to changing the molar ratio of lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4), the halide solid electrolyte Li 1.65 Ta 0.35 Zr 0.65 Cl6.

[0088] Example 4

[0089] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0090] In addition to changing the molar ratio of lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4), the halide solid electrolyte Li 1.6 Ta 0.4 Zr 0.6 Cl6.

[0091] Example 5

[0092] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0093] In addition to changing the molar ratio of lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4), the halide solid electrolyte Li 1.72 Ta 0.28 Zr 0.72 Cl6.

[0094] Example 6

[0095] This example is used to illustrate the preparation method of the halide solid electrolyte of the present invention.

[0096] In addition to changing the molar ratio of lithium source (LiCl), tantalum source (TaCl5) and zirconium source (ZrCl4), the halide solid electrolyte Li 1.75 Ta 0.25 Zr 0.75 Cl6.

[0097] Test Example 1

[0098] (1) The halide solid electrolytes obtained in Examples 1-4 and Comparative Examples 1-2 were characterized by XRD (Smartlab 9kw). The results are shown in FIG1 .

[0099] It can be seen from FIG1 that the halide solid electrolytes (Examples 1-4 and Comparative Example 2) after tantalum doping basically maintain the original crystal structure of the Li2ZrCl6 solid electrolyte.

[0100] (2) Impedance test

[0101] Impedance tests were performed on the halide solid electrolytes obtained in Examples 1-6 and Comparative Examples 1-2.

[0102] The test procedure is as follows: halide solid electrolyte powder is loaded into an electrically insulating cylindrical cell with an inner diameter of 10 mm. The powder is then compressed at 300 MPa, sandwiched between two stainless steel electrodes. The sample weight is approximately 100 mg, and the thickness of the compressed powder is measured using a vernier caliper.

[0103] The ionic conductivity value is calculated by the following formula:

[0104] Where L is the thickness of the sample powder, R is the resistance value obtained by EIS (electrochemical impedance spectroscopy) measurement, and S is the surface area of ​​the sample.

[0105] The ionic conductivity results of each halide solid electrolyte are shown in FIG2 and Table 1.

[0106] Table 1

[0107] As can be seen from Figure 2 and Table 1, the high-valent cation element Ta is selected to dope the halide solid electrolyte Li2ZrCl6, and the method of generating anion gaps or cation vacancies is used to improve the ionic conductivity of the solid electrolyte. When the Ta doping amount is 0.28, the halide solid electrolyte Li 1.72 Ta 0.28 Zr 0.72 The ionic conductivity of Cl6 at room temperature can reach a maximum value of 1.53×10 -3 mS·cm -1 .

[0108] (3) Linear sweep voltammetry test

[0109] Four samples were prepared according to the method of Example 5 and subjected to linear sweep voltammetry tests. The results are shown in FIG3 .

[0110] The specific testing process is as follows: The halide solid electrolyte powder is loaded into an electrically insulating cylindrical cell with an inner diameter of 10 mm and then compressed at 300 MPa. The powder is sandwiched between a stainless steel electrode and a lithium-indium alloy. Linear sweep voltammetry is performed using an electrochemical workstation with a scan rate of 0.1 mV / s and a scan range of 0-6 V.

[0111] From Figure 3 we can see that Li 1.72 Ta 0.28 Zr 0.72 The electrochemical window of Cl6 solid electrolyte reaches above 5.5V, which can be well adapted to high-voltage positive electrodes.

[0112] The representative examples are intended to help illustrate the present invention and are not intended to, and should not be construed as, limiting the scope of the present invention. Indeed, various modifications of the present invention and many other embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art, including the examples and the scientific and patent literature references cited herein. The examples contain important additional information, illustrations, and guidance that can be employed in the practice of the present invention in its various embodiments and equivalents.

Claims

1. A halide solid electrolyte, characterized in that, The chemical formula of the halide solid electrolyte is as shown in the formula Li 2-x Ta x Zr 1-x Cl6, where x is 0.2 - 0.

4.

2. The halide solid electrolyte according to claim 1, wherein, x is 0.25 - 0.3, preferably 0.27 - 0.

29.

3. The halide solid electrolyte according to claim 1 or 2, wherein, The halide solid electrolyte is prepared by mixing and grinding a lithium source LiCl, a zirconium source ZrCl4, and a tantalum source TaCl5.

4. The halide solid electrolyte according to claim 3, wherein The rotation speed of the grinding is 450 - 700 rpm. Preferably, the grinding is ball milling or sand milling.

5. A method for preparing a halide solid electrolyte, characterized in that, The preparation method includes the following steps: (1) Weigh the lithium source LiCl, the zirconium source ZrCl4, and the tantalum source TaCl5 according to the molar ratio of (2 - x):(1 - x):x, where x is 0.2 - 0.4; (2) Mix and grind the lithium source LiCl, the zirconium source ZrCl4, and the tantalum source TaCl5 obtained in step (1) to obtain a halide solid electrolyte; Among them, in step (2), the rotation speed of the grinding is 450 - 700 rpm.

6. The preparation method according to claim 5, wherein, x is 0.25 - 0.3, preferably 0.27 - 0.

29.

7. The preparation method according to claim 5 or 6, wherein In step (2), the rotation speed of the grinding is 550 - 650 rpm; and / or The total grinding time is 5 - 20 h, preferably 8 - 15 h; and / or The grinding is carried out in an intermittent manner. Preferably, it is ground for 10 - 15 min and paused for 3 - 10 min.

8. The preparation method according to claim 7, wherein the grinding is ball milling or sand milling.

9. The preparation method according to claim 8, wherein the ball-to-material ratio of the ball milling is 30 - 50:1, preferably 35 - 45:1; and / or The ball milling uses zirconia - based milling beads, and the diameter of the milling beads is 3 - 10 mm.

10. The preparation method according to any one of claims 5-9, wherein, Both step (1) and step (2) are carried out in an inert atmosphere, preferably in an argon atmosphere.

11. The preparation method according to any one of claims 5-10, wherein, The preparation method does not include a heat treatment step.

12. The application of the halide solid electrolyte according to any one of claims 1 - 4 or the halide solid electrolyte prepared by the preparation method according to any one of claims 5 - 11 in a battery, preferably a lithium - ion battery.

13. A solid electrolyte layer, characterized in that, The solid electrolyte layer contains the halide solid electrolyte according to any one of claims 1 - 4 or the halide solid electrolyte prepared by the preparation method according to any one of claims 5 - 11.

14. A battery, comprising a solid electrolyte layer, a positive electrode and a negative electrode, characterized in that, At least one of the solid electrolyte layer, the positive electrode, and the negative electrode contains the halide solid electrolyte according to any one of claims 1 - 4 or the halide solid electrolyte prepared by the preparation method according to any one of claims 5 - 11.

15. A solid electrolyte battery, which includes a solid electrolyte layer, a positive electrode, and a negative electrode, is characterized in that, The solid electrolyte layer contains the halide solid electrolyte according to any one of claims 1 - 4 or the halide solid electrolyte prepared by the preparation method according to any one of claims 5 - 11.

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