Acid chloride solid electrolytes, methods for producing the same, and their applications

Abstract

This invention relates to the field of all-solid-state lithium battery materials and provides acid chloride solid electrolytes, methods for producing the same, and their applications. [Solution] The general formula for this acid chloride solid electrolyte is xLi2O-(1-y)ZrCl4-yAlCl3 (where 0

Description

[Technical Field]

[0001] This invention relates to the technical field of all-solid-state lithium battery materials, and more particularly to acid chloride solid electrolytes, methods for producing the same, and applications thereof. [Background technology]

[0002] As a next-generation energy storage technology, the application of all-solid-state lithium batteries is expected to solve the safety and energy density problems inherent in conventional lithium-ion batteries. Currently, no single solid electrolyte exists that meets all the requirements necessary for commercialization, including high ionic conductivity, excellent mechanical deformability, and cost-effectiveness. Due to the lack of these crucial properties, inorganic solid electrolytes reported to date suffer from challenges such as low ion transport efficiency, poor contact at electrode interfaces, and high manufacturing costs, which significantly hinder the practical application of all-solid-state lithium batteries.

[0003] Unlike conventional lithium-ion batteries, liquid electrolytes can easily penetrate the electrodes and provide sufficient ionic conductivity, but solid-state batteries must build an ion percolation network within the electrodes by relying on solid-state contact between electrolyte particles. To form good solid-state contact under pressure with commercially available positive electrode active material particles such as brittle high-nickel ternary oxides or lithium iron phosphate, the solid electrolyte needs to have the lowest possible Young's modulus. However, as brittle materials, the Young's modulus of oxide electrolytes generally exceeds 100 GPa (for example, Li 0.33 La 0.56 TiO3:~200GPa;Li7La3Zr2O 12 :~156GPa;Li 1.5 Al 0.5 Ge 1.5 P3O 12 (~115 GPa), this requirement cannot be met. In contrast, sulfides and chlorides have some machinability, but their mechanical properties are still not sufficient. For example, typical sulfide electrolytes Li6PS5Cl and Li 10 GeP2S12 The Young's moduli are 25.2 GPa and 26.7 GPa respectively, and the Young's moduli of typical chloride electrolytes Li3YCl6, Li2ZrCl6 and Li3InCl6 are 45.75 GPa, 22.5 GPa and 19.8 GPa respectively. However, in order to achieve good solid-solid contact, the solid electrolyte needs to have a Young's modulus of 10 GPa or less (Non-Patent Document 1: ACS Appl. Energy Mater. 2023, 6, 9615-9623). In addition to an extremely low Young's modulus, the solid electrolyte also needs to have a sufficiently high ionic conductivity (higher than 1 mS·cm at 25 °C), and expensive compounds such as Li2S and rare earth chlorides cannot be used as raw materials (otherwise, high costs will prevent commercialization). However, currently, inorganic solid electrolytes that simultaneously meet the above requirements, especially those with a Young's modulus of less than 10 GPa, are extremely rare. -1 -1

[0004] Therefore, it is extremely important to provide an oxychloride solid electrolyte with an extremely low Young's modulus, high ionic conductivity and low cost.

Prior Art Documents

Non-Patent Documents

[0005]

Non-Patent Document 1

Summary of the Invention

[0006] An object of the present invention is to provide an oxychloride solid electrolyte, a manufacturing method thereof, and an application thereof in order to solve technical problems such as the difficulty in achieving both a low Young's modulus and high ionic conductivity in the existing technology, and the high manufacturing cost.

[0007] To achieve the above object, the present invention provides the following technical solutions:

[0008] The present invention provides the above-mentioned oxychloride solid electrolyte having a chemical general formula of xLi2O-(1-y)ZrCl4-yAlCl3 (where 0 < x ≤ 3, 0 < y ≤ 1).

[0009] TIFF2026114946000002.tif29166

[0010] The present invention provides a method for producing the above-mentioned oxychloride solid electrolyte, including the step of obtaining the oxychloride solid electrolyte by mixing Li2O, ZrCl4 and AlCl3 and then performing high-energy ball milling.

[0011] Furthermore, the molar ratio of Li2O, ZrCl4 and AlCl3 is 0.5 - 2:0.4 - 0.9:0.1 - 0.6.

[0012] Furthermore, the mixing time is 20 - 40 minutes.

[0013] Furthermore, the mass ratio of balls to raw materials in the high-energy ball milling is 10 - 45:1, the rotation speed of the high-energy ball milling is 150 - 550 rpm, and the time of the high-energy ball milling is 2 - 40 hours.

[0014] The present invention further provides the application of the above-mentioned oxychloride solid electrolyte to an all-solid-state lithium battery.

[0015] Beneficial effects of the present invention:

[0016] 1) The oxychloride solid electrolyte, which is highly amorphous xLi2O-(1-y)ZrCl4-yAlCl3 produced by the present invention, has a low Young's modulus (less than 4 GPa, significantly lower than 10 - 100 GPa of many other solid electrolytes) and a high ionic conductivity (higher than 1 mS·cm at 25°C), and has advantages such as not requiring expensive compounds as raw materials. -1 Higher), and has advantages such as not requiring expensive compounds as raw materials.

[0017] 2) The acid chloride solid electrolyte xLi2O-(1-y)ZrCl4-yAlCl3 produced in the present invention has an anionic skeleton in which Zr-O / Cl and / or Al-O / Cl polyhedra are formed by ideal O / Cl angle sharing, has a Young's modulus as low as 1.41 GPa at room temperature, and an ionic conductivity of 2.55 mS·cm -1 It is high up to this point. Therefore, xLi2O-(1-y)ZrCl4-yAlCl3 electrolyte and high nickel positive electrode (LiNi 0.92 Co 0.06 Mn 0.02 High-voltage all-solid-state batteries using O2 (abbreviated as scNCM92) exhibit excellent electrochemical properties (capacity retention rate of over 80% even after >4000 cycles).

[0018] 3) The synthesis of the xLi2O-(1-y)ZrCl4-yAlCl3 acid chloride solid electrolyte produced by the present invention does not require expensive raw materials such as Li2S and / or rare earth compounds, offering significant cost advantages and promising prospects for commercialization. [Brief explanation of the drawing]

[0019] [Figure 1] This is the X-ray diffraction pattern of 1,0Li2O-0.8ZrCl4-0.2AlCl3 produced in Example 1. [Figure 2] This is the electrochemical impedance diagram of 1,0Li2O-0.8ZrCl4-0.2AlCl3 produced in Example 1. [Figure 3] This is the DC polarization diagram of 1.0Li2O-0.8ZrCl4-0.2AlCl3 produced in Example 1. [Figure 4] This is the Young's modulus distribution diagram for 1,0Li2O-0.8ZrCl4-0.2AlCl3 produced in Example 1. [Figure 5] This is the X-ray diffraction pattern of 1,8Li2O-0,8ZrCl4-0.2AlCl3 produced in Example 2. [Figure 6] This is the electrochemical impedance diagram of 1,8Li2O-0,8ZrCl4-0,2AlCl3 produced in Example 2. [Figure 7]This is the DC polarization diagram of 1,8Li2O-0,8ZrCl4-0.2AlCl3 produced in Example 2. [Figure 8] This is the Young's modulus distribution diagram for 1,8Li2O-0,8ZrCl4-0.2AlCl3 produced in Example 2. [Figure 9] This is the X-ray diffraction pattern of 1,0Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 3. [Figure 10] This is the electrochemical impedance diagram of 1,0Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 3. [Figure 11] This is the DC polarization diagram of 1.0Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 3. [Figure 12] This is the X-ray diffraction pattern of 1,4Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 4. [Figure 13] This is the electrochemical impedance of 1,4Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 4. [Figure 14] This is the DC polarization diagram of 1,4Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 4. [Figure 15] This is the Young's modulus distribution diagram for 1,4Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 4. [Figure 16] This is a diagram illustrating the long-term cycle performance at a 10C (2000mA·g-1) rate for the Li-In|Li6PS5Cl-1.4Li2O-0.75ZrCl4-0.25AlCl3|scNCM92 battery assembled from 1,4Li2O-0.75ZrCl4-0.25AlCl3 manufactured in Example 4. [Figure 17] (a) and the corresponding charge-discharge curve diagram (b) show the long-term cycle performance of the Li-In|Li6PS5Cl-1.4Li2O-0.75ZrCl4-0.25AlCl3|scNCM92 battery assembled from 1,4Li2O-0.75ZrCl4-0.25AlCl3 manufactured in Example 4, at a rate of 0.1C (20mA·g-1) and high active material load. [Figure 18] This is the X-ray diffraction pattern of 1,8Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 5. [Figure 19] This is the electrochemical impedance of 1,8Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 5. [Figure 20] This is the DC polarization diagram of 1,8Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 5. [Figure 21] This is the X-ray diffraction pattern of 1,0Li2O-0.7ZrCl4-0.3AlCl3 produced in Example 6. [Figure 22] This is the electrochemical impedance of 1,0Li2O-0.7ZrCl4-0.3AlCl3 produced in Example 6. [Figure 23] This is the DC polarization diagram of 1.0Li2O-0.7ZrCl4-0.3AlCl3 produced in Example 6. [Figure 24] This is the Young's modulus distribution diagram for 1.0Li2O-0.7ZrCl4-0.3AlCl3 produced in Example 6. [Figure 25] This is the X-ray diffraction pattern of 1,0Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 7. [Figure 26] This is the electrochemical impedance of 1,0Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 7. [Figure 27] This is the DC polarization diagram of 1.0Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 7. [Figure 28] This is the Young's modulus distribution diagram for 1.0Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 7. [Figure 29] This is the X-ray diffraction pattern of 1,8Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 8. [Figure 30] This is the electrochemical impedance of 1,8Li2O-0.5ZrCl4-0.5AlCl3 produced in Example 8. [Figure 31]It is the DC polarization diagram of 1.8Li2O - 0.5ZrCl4 - 0.5AlCl3 manufactured in Example 8. [Figure 32] It is the Young's modulus distribution diagram of 1.8Li2O - 0.5ZrCl4 - 0.5AlCl3 manufactured in Example 8.

Embodiments for Carrying Out the Invention

[0020] The present invention provides an oxychloride solid electrolyte. The chemical general formula of the oxychloride solid electrolyte is xLi2O-(1 - y)ZrCl4 - yAlCl3 (where 0 < x ≤ 3, 0 < y ≤ 1, preferably 0.5 < x ≤ 2, 0.1 < y ≤ 0.6, more preferably 1 ≤ x ≤ 1.8, 0.2 ≤ y ≤ 0.5).

[0021] TIFF2026114946000003.tif35166

[0022] The present invention provides a method for manufacturing the oxychloride solid electrolyte, which includes the step of obtaining the oxychloride solid electrolyte by mixing Li2O, ZrCl4 and AlCl3 and then performing high - energy ball milling.

[0023] In the present invention, the molar ratio of Li2O, ZrCl4 and AlCl3 is 0.5 - 2:0.4 - 0.9:0.1 - 0.6, preferably 0.7 - 1.9:0.45 - 0.85:0.15 - 0.55, more preferably 1 - 1.8:0.5 - 0.8:0.2 - 0.5.

[0024] In the present invention, the mixing time is 20 - 40 minutes, preferably 25 - 35 minutes, more preferably 30 minutes.

[0025] In the present invention, the mass ratio of balls to raw material in the high-energy ball milling is 10 to 45:1, preferably 15 to 40:1, more preferably 20 to 25:1, the rotational speed of the high-energy ball milling is 150 to 550 rpm, preferably 250 to 500 rpm, more preferably 500 rpm, and the duration of the high-energy ball milling is 2 to 40 hours, preferably 5 to 30 hours, more preferably 20 to 30 hours.

[0026] The present invention further provides the application of the acid chloride solid electrolyte to all-solid-state lithium batteries.

[0027] The technical solutions provided by the present invention will be described in detail below with reference to examples, but these examples will not limit the scope of the present invention.

[0028] Example 1 In a glove box protected by argon (moisture and oxygen content less than 0.01 ppm), Li2O, ZrCl4, and AlCl3 in a molar ratio of 1:0.8:0.2 are mixed in an agate mortar for 30 minutes. After mixing, the mixture is transferred to an 80 mL zirconia ball mill. The diameter of the zirconia balls is 5 mm, and the mass ratio of balls to raw materials is 20:1. High-energy ball milling is performed at a rotation speed of 500 rpm for 30 hours in a Fritsch Pulverisette 7 high-energy ball mill manufactured in Germany to obtain a 1,0Li2O-0.8ZrCl4-0.2AlCl3 acid chloride solid electrolyte with a crystalline phase proportion of 20% or less. However, the crystalline phase is monoclinic and the space group is C2 / m.

[0029] The X-ray diffraction pattern, electrochemical impedance diagram, DC polarization diagram, and Young's modulus distribution of the acid chloride solid electrolyte produced in Example 1 were measured, and the measurement results are shown in Figures 1 to 4, respectively. As can be seen from Figures 1 to 4, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 1 is shown. i ) is 1.98 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 1.72 × 10 -9 S·cm-1 The fact that its ionic conductivity is six orders of magnitude higher than its electronic conductivity proves that 1.0Li2O-0.8ZrCl4-0.2AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1.0Li2O-0.8ZrCl4-0.2AlCl3 is 2.47 GPa, indicating that this electrolyte has good mechanical deformation capability.

[0030] Example 2 In Example 2, the molar ratio of Li2O, ZrCl4, and AlCl3 was 1.8:0.8:0.2, and all other conditions were the same as in Example 1, yielding a 1,8Li2O-0.8ZrCl4-0.2AlCl3 acid chloride solid electrolyte in which the crystalline phase accounted for 20% or less. However, the crystalline phase was monoclinic and the space group was C2 / m.

[0031] The X-ray diffraction pattern, electrochemical impedance diagram, DC polarization diagram, and Young's modulus distribution of the acid chloride solid electrolyte produced in Example 2 were measured, and the measurement results are shown in Figures 5 to 8, respectively. As can be seen from Figures 5 to 8, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 2 is shown. i ) is 0.624 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 5.61 × 10 -10 S·cm -1 The fact that its ionic conductivity is six orders of magnitude higher than its electronic conductivity proves that 1,8Li2O-0,8ZrCl4-0,2AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1,8Li2O-0,8ZrCl4-0,2AlCl3 is 3.98 GPa, indicating that this electrolyte has good mechanical deformation capability.

[0032] TIFF2026114946000004.tif42166

[0033] The X-ray diffraction pattern, electrochemical impedance diagram, and DC polarization diagram of the acid chloride solid electrolyte produced in Example 3 were measured, and the measurement results are shown in Figures 9 to 11, respectively. As can be seen from Figures 9 to 11, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 3 is i ) is 2.01 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 2.7 × 10 -9 S·cm -1 The fact that its ionic conductivity is five orders of magnitude higher than its electronic conductivity proves that 1,0Li2O-0.75ZrCl4-0.25AlCl3 can be used as a pure ionic conductor in solid-state batteries.

[0034] TIFF2026114946000005.tif42166

[0035] The X-ray diffraction pattern, electrochemical impedance diagram, and DC polarization diagram of the acid chloride solid electrolyte produced in Example 4 were measured, and the measurement results are shown in Figures 12 to 15, respectively. As can be seen from Figures 12 to 15, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 4 is shown. i ) is 2.55 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 3.09 × 10 -9 S·cm -1 The fact that its ionic conductivity is five orders of magnitude higher than its electronic conductivity proves that 1,4Li2O-0.75ZrCl4-0.25AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1,4Li2O-0.75ZrCl4-0.25AlCl3 is 1.41 GPa, indicating that this electrolyte has good mechanical deformation capability.

[0036] All-solid-state lithium batteries are assembled in a glove box (moisture and oxygen content less than 0.01 ppm) under argon protection. The composite positive electrode is made of single-crystal LiNi 0.92 Co 0.06 Mn 0.02The 1,4Li2O-0.75ZrCl4-0.25AlCl3 produced in Example 4 by O2 was manufactured by mixing the powders at 1500 rpm for 15 minutes using a vortex oscillator mixer in a mass ratio of 75:25. The steps for assembling the all-solid-state lithium battery are to first cold-press 25 mg of 1,4Li2O-0.75ZrCl4-0.25AlCl3 powder in a 10 mm diameter peak mold at a pressure of 150 MPa and hold for 1 minute, and then to process 5-30 mg·cm². -2 The composite positive electrode with a load of 5-6 mg·cm³ was dispersed on one side of the 1.4Li2O-0.75ZrCl4-0.25AlCl3 layer and held under a pressure of 300 MPa for 5 minutes. Next, to avoid side reactions between the 1.4Li2O-0.75ZrCl4-0.25AlCl3 and the negative electrode, 35 mg of Li6PS5Cl sulfide powder was uniformly dispersed on the opposite side of the 1.4Li2O-0.75ZrCl4-0.25AlCl3 layer and held under a pressure of 150 MPa for 1 minute. Finally, the negative electrode Li-In was pressed onto one side of the Li6PS5Cl, and an external pressure of 190 MPa was applied to the entire battery. The assembled all-solid-state lithium battery was measured, and the measurement results are shown in Figures 16 and 17, respectively. As can be seen from Figures 16 and 17, the load was 5-6 mg·cm³. -2 Under the load of conventional positive electrode active materials, this all-solid-state battery is 10C (2000mA·g). -1 After 4208 cycles, the capacity retention rate reaches 80%. The load of the positive electrode active material is 20 mg·cm. -2 If it exceeds 0.1C (20mA·g), this all-solid-state battery will be 0.1C (20mA·g -1 After 20 cycles, the capacity retention rate was 4.22mAh·cm². -2 (Capacity retention rate reaches 98.18%).

[0037] Example 5 In Example 5, the molar ratio of Li2O, ZrCl4, and AlCl3 was 1.8:0.75:0.25, and all other conditions were the same as in Example 1, yielding a 1.8Li2O-0.75ZrCl4-0.25AlCl3 acid chloride solid electrolyte in which the crystalline phase accounted for 20% or less. However, the crystalline phase was monoclinic and the space group was C2 / m.

[0038] The X-ray diffraction pattern, electrochemical impedance diagram, and DC polarization diagram of the acid chloride solid electrolyte produced in Example 5 were measured, and the measurement results are shown in Figures 18 to 20, respectively. As can be seen from Figures 18 to 20, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 5 is shown. i ) is 0.733 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 1.22 × 10 -9 S·cm -1 The fact that its ionic conductivity is five orders of magnitude higher than its electronic conductivity proves that 1,8Li2O-0.75ZrCl4-0.25AlCl3 can be used as a pure ionic conductor in solid-state batteries.

[0039] TIFF2026114946000006.tif42166

[0040] The X-ray diffraction pattern, electrochemical impedance diagram, DC polarization diagram, and Young's modulus distribution diagram of the acid chloride solid electrolyte produced in Example 6 were measured, and the measurement results are shown in Figures 21 to 24, respectively. As can be seen from Figures 21 to 24, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 6 is shown. i ) is 1.74 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 3.27 × 10 -9 S·cm -1 The fact that its ionic conductivity is five orders of magnitude higher than its electronic conductivity proves that 1.0Li2O-0.7ZrCl4-0.3AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1.0Li2O-0.7ZrCl4-0.3AlCl3 is 3.65 GPa, indicating that this electrolyte has good mechanical deformation capability.

[0041] TIFF2026114946000007.tif42166

[0042] The X-ray diffraction pattern, electrochemical impedance diagram, and DC polarization diagram of the acid chloride solid electrolyte produced in Example 7 were measured, and the measurement results are shown in Figures 25 to 28, respectively. As can be seen from Figures 25 to 28, the room temperature ionic conductivity (σ) of the acid chloride solid electrolyte produced in Example 7 is shown. i ) is 0.846 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 4.06 × 10 -9 S·cm -1 The fact that its ionic conductivity is five orders of magnitude higher than its electronic conductivity proves that 1.0Li2O-0.5ZrCl4-0.5AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1.0Li2O-0.5ZrCl4-0.5AlCl3 is 3.01 GPa, indicating that this electrolyte has good mechanical deformation capability.

[0043] Example 8 In Example 8, the molar ratio of Li2O, ZrCl4, and AlCl3 was 1.8:0.5:0.5, and all other conditions were the same as in Example 1, yielding a 1,8Li2O-0.5ZrCl4-0.5AlCl3 acid chloride solid electrolyte in which the crystalline phase accounted for 20% or less. However, the crystalline phase was monoclinic and the space group was C2 / m.

[0044] The X-ray diffraction pattern, electrochemical impedance diagram, DC polarization diagram, and Young's modulus distribution diagram of the acid chloride solid electrolyte produced in Example 8 were measured, and the measurement results are shown in Figures 29 to 32, respectively. As can be seen from Figures 29 to 32, the room temperature ionic conductivity (σ) of the solid electrolyte produced in Example 8 is i ) is 0.367 mS·cm -1 And the room temperature electronic conductivity (σ e ) is 1.68 × 10 -9 S·cm -1Moreover, the fact that the ionic conductivity is five orders of magnitude higher than the electronic conductivity proves that 1.8Li2O-0.5ZrCl4-0.5AlCl3 can be used as a pure ionic conductor in solid-state batteries. At the same time, the Young's modulus of 1.8Li2O-0.5ZrCl4-0.5AlCl3 is 3.84 GPa, indicating that this electrolyte has good mechanical deformation ability.

[0045] As can be seen from the above examples, the present invention provides an oxychloride solid electrolyte with a chemical general formula of xLi2O-(1-y)ZrCl4-yAlCl3 (where 0 < x ≤ 3, 0 < y ≤ 1), a method for manufacturing the same, and its applications. Compared with other solid electrolytes such as sulfides, halides, and oxides (the Young's modulus of most of them exceeds 20 GPa and even exceeds 100 GPa), the oxychloride solid electrolyte in the present invention has a lower Young's modulus (≤ 4 GPa). The all-solid-state lithium battery assembled using the oxychloride solid electrolyte in the present invention has excellent surface capacity and long-term cycle stability.

[0046] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above-described embodiments. Those skilled in the art can make various changes and improvements without departing from the principle of the present invention, and these are also included in the protection scope of the present invention.

Claims

1. Acid chloride solid electrolytes, A solid electrolyte characterized by its acid chloride properties.

2. A method for producing an acid chloride solid electrolyte according to claim 1, Li ２ O, ZrCl ４ and AlCl ３ The process includes the step of obtaining an acid chloride solid electrolyte by mixing the ingredients and then subjecting them to high-energy ball milling. A method for producing an acid chloride solid electrolyte, characterized by the following features.

3. The Li ２ O, ZrCl ４ and AlCl ３ The molar ratio is 0.5–2:0.4–0.9:0.1–0.

6. A method for producing an acid chloride solid electrolyte according to claim 2.

4. The mixing time is 20 to 40 minutes. A method for producing an acid chloride solid electrolyte according to claim 3.

5. In the aforementioned high-energy ball milling, the mass ratio of balls to raw material is 10 to 45:1, the rotational speed of the high-energy ball milling is 150 to 550 rpm, and the duration of the high-energy ball milling is 2 to 40 hours. A method for producing an acid chloride solid electrolyte according to claim 4.

6. Use of the acid chloride solid electrolyte described in claim 1 in an all-solid-state lithium battery.

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