Method for producing material for solid electrolyte, and material for solid electrolyte

Abstract

Disclosed is a method for producing a material for a solid electrolyte, the method including: a step for preparing a mixed starting material, wherein the mixed starting material has an Li source, a B source, an M source, and an O source, and M is at least one element that is selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr; a step for heating the mixed starting material to 930°C or higher so as to obtain a melt; and a step for cooling the melt so as to obtain an amorphous material that is represented by general formula LixByMzO7, where 2 ≤ x ≤ 3, y > 0, z ≥ 0.06, and 3 ≤ y + z ≤ 4.

Description

Method for manufacturing a material for a solid electrolyte, and material for a solid electrolyte

[0001] The present invention relates to a method for producing a material for a solid electrolyte, and to a material for a solid electrolyte.

[0002] In recent years, efforts to become carbon neutral have been attracting attention, especially in the automotive industry. ２ To reduce emissions, the electrification of automobiles is progressing, and this is accelerating research and development into safe and highly energy-efficient secondary batteries, such as all-solid-state batteries.

[0003] In all-solid-state batteries, the performance of the solid electrolyte can be a key technology, so research and development of new materials with high ionic conductivity is progressing worldwide.

[0004] For example, Patent Document 1 discloses Li ２ B ４ O ７ The materials contained water and Li(FSO ２ ) ２ It is described that a powder mixture prepared by adding an N electrolyte salt has high conductivity (Patent Document 1).

[0005] International Publication No. 2022 / 118870

[0006] However, the method for producing the powder mixture described in Patent Document 1 does not include the step of forming crystalline Li ２ B ４ O ７ This method involves a step of ball milling the material for 100 hours. This method requires a long time to produce the material, resulting in poor production efficiency and making it difficult to say that it is a method that can be adopted industrially.

[0007] Therefore, there is still a need for a material for a solid electrolyte that can be suitably applied to all-solid-state batteries, and a method for producing the same.

[0008] The present invention has been made in view of the above background, and an object of the present invention is to provide a method for more efficiently producing a material applicable to a solid electrolyte, and to provide a material applicable to a solid electrolyte that can be produced by such a method.

[0009] The present invention provides a method for producing a material for a solid electrolyte, comprising: (1) a step of preparing a mixed raw material, the mixed raw material having a lithium (Li) source, a boron (B) source, an M source, and an oxygen (O) source, wherein the M is at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, the mixed raw material being: (i) a combination of three types of compounds, namely, a compound (a) containing Li, a compound (b) containing B, and a compound (c) containing M, wherein at least one of (a), (b), and (c) is an oxide, or (ii) a combination of two types of compounds, namely, a compound (d) containing Li and B, and a compound (c) containing M, wherein at least one of (d) and (c) is an oxide, or (iii) a combination of two types of compounds, namely, a Li compound (a) and a compound (e) containing B and M, wherein at least one of (a) and (e) is an oxide, (2) a step of heating the mixed raw material to 930°C or higher to obtain a melt; and (3) a step of cooling the melt to obtain an amorphous material, wherein the amorphous material is selected from the group consisting of a compound represented by the following general formula: ｘ B ｙ M ｚ O ７ (1) where 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4.

[0010] The present invention also provides a material for a solid electrolyte, which is amorphous and has the following general formula: Li ｘ B ｙ M ｚ O ７ (1) wherein M includes at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, and 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4; and a material for a solid electrolyte is provided, which includes M in a glass structure.

[0011] The present invention can provide a method for more efficiently producing a material applicable to a solid electrolyte, and also can provide a material applicable to a solid electrolyte that can be produced by such a method.

[0012] 1 is a diagram schematically illustrating a flow of a method for producing a material for a solid electrolyte according to an embodiment of the present invention, FIG. 2 is a diagram illustrating an X-ray diffraction chart of a material for a solid electrolyte (Sample 1) according to an embodiment of the present invention, and FIG. 3 is a diagram illustrating an X-ray diffraction chart of a material for a solid electrolyte (Sample 11) of a related art.

[0013] An embodiment of the present invention will be described below.

[0014] As described above, in the method for producing a solid electrolyte material described in Patent Document 1, crystalline Li ２ B ４ O ７ The material must be ball milled for 100 hours, and such a manufacturing method requires a long time to manufacture the material, resulting in poor manufacturing efficiency and making it difficult to say that it is a method that can be adopted industrially.

[0015] In contrast, one embodiment of the present invention provides a method for producing a material for a solid electrolyte, comprising: (1) preparing a mixed raw material; the mixed raw material having a lithium (Li) source, a boron (B) source, an M source, and an oxygen (O) source, wherein M is at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr; the mixed raw material is: (i) a combination of three types of compounds, namely, a compound (a) containing Li, a compound (b) containing B, and a compound (c) containing M, wherein at least one of (a), (b), and (c) is an oxide; or (ii) a combination of two types of compounds, namely, a compound (d) containing Li and B, and a compound (c) containing M, wherein at least one of (d) and (c) is an oxide; or (iii) a combination of two types of compounds, namely, a Li compound (a) and a compound (e) containing B and M, wherein at least one of (a) and (e) is an oxide; (2) a step of heating the mixed raw material to 930°C or higher to obtain a melt; and (3) a step of cooling the melt to obtain an amorphous material, wherein the amorphous material is selected from the group consisting of a compound represented by the following general formula: ｘ B ｙ M ｚ O ７ (1) where 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4.

[0016] In one embodiment of the present invention, a material for a solid electrolyte can be obtained by the steps of: (1) heating the mixed raw material prepared in step (1) to 930°C or higher to obtain a melt; and (2) cooling the obtained melt. For example, in one embodiment of the present invention, a material for a solid electrolyte can be obtained by rapidly cooling the melt.

[0017] In addition, pure crystalline Li without additives ２ B ４ O ７ It is difficult to make the material amorphous even after going through the steps (1) and (2) above.

[0018] However, in one embodiment of the present invention, pure Li ２ B ４ O ７ Li-based materials are not the same as those containing the element M. ２ B ４ O ７ It is expected that the additional element M is substituted at the site of the atom B.

[0019] In the material system according to one embodiment of the present invention, an amorphous material can be obtained by the steps (1) and (2) above.

[0020] Due to these characteristics, in one embodiment of the present invention, a material applicable to a solid electrolyte can be produced more efficiently, and therefore, the method according to one embodiment of the present invention can also be applied to industrial production of materials for solid electrolytes.

[0021] In one embodiment of the present invention, a material for a solid electrolyte is provided, which is amorphous and has the following general formula: Li ｘ B ｙ M ｚ O ７ (1) wherein M includes at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, and 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4; and a material for a solid electrolyte is provided, which includes M in a glass structure.

[0022] The "material for a solid electrolyte" according to one embodiment of the present invention has a function of forming the skeleton of a solid electrolyte. However, the "material for a solid electrolyte" according to one embodiment of the present invention does not have good ionic conductivity by itself.

[0023] Therefore, when actually producing a solid electrolyte, the "material for a solid electrolyte" according to one embodiment of the present invention is used in combination with other components, particularly components that exhibit ionic conductivity, such as an electrolyte salt.

[0024] In this case, the "material for a solid electrolyte" according to one embodiment of the present invention constitutes a skeleton for the solid electrolyte, and an electrolyte salt is dispersed and filled inside this skeleton, thereby forming an ion conduction path within the skeleton. This makes it possible to form a solid electrolyte containing the "material for a solid electrolyte" according to one embodiment of the present invention.

[0025] Furthermore, the "solid electrolyte material" according to one embodiment of the present invention is an amorphous material. By making the "solid electrolyte material" according to one embodiment of the present invention amorphous, electrolyte salts and the like are more likely to be arranged at the interface of the "solid electrolyte material," and more ion conduction paths can be formed inside the skeleton.

[0026] (Material for Solid Electrolyte According to One Embodiment of the Present Invention) Next, the material for solid electrolyte according to one embodiment of the present invention will be described in more detail.

[0027] As described above, the material for a solid electrolyte according to one embodiment of the present invention (hereinafter referred to as the "first material") is a material represented by the general formula (1): Li ｘ B ｙ M ｚ O ７ (1) is an amorphous material represented by the formula:

[0028] Here, M includes at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, and 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4.

[0029] In the first material, the element M serves as a network former of glass. Therefore, the element M is preferably at least one of Al and Si, which are expected to have a higher effect as a network former.

[0030] Furthermore, x is preferably in the range of 2≦x≦2.5, and more preferably 2.

[0031] Preferably, y is in the range of 2≦y≦4.5, and more preferably in the range of 3.5≦y≦3.93.

[0032] z is 0.06 or more. In particular, when M is Al, z > 0.07 and z > 0.08 are preferable. Furthermore, when M is Si, z > 0.11 and z > 0.12 are preferable.

[0033] The general formula (1) is, for example, Li ２ B ４－ｚ (Al, Si) ｚ O ７ It may be expressed as:

[0034] In the present application, whether a target material is amorphous can be determined from the results of X-ray diffraction. That is, if a halo pattern without a 2θ diffraction peak is observed in the X-ray diffraction results, the material to be evaluated is determined to be amorphous.

[0035] As mentioned above, the term "material for a solid electrolyte" in this application does not mean a material that can be used alone as a solid electrolyte for a secondary battery. The term "material for a solid electrolyte" refers to a material that is used as a base (skeleton) that provides a path for ion conduction when producing a solid electrolyte.

[0036] (Method for Producing a Material for a Solid Electrolyte According to an Embodiment of the Present Invention) Next, a method for producing a material for a solid electrolyte according to an embodiment of the present invention will be described in more detail with reference to the drawings.

[0037] FIG. 1 shows a schematic flow of a method for producing a material for a solid electrolyte according to one embodiment of the present invention (hereinafter referred to as "first method").

[0038] As shown in FIG. 1 , the first method includes a step of preparing a mixed raw material (step S110), a step of heating the mixed raw material to 930° C. or higher to obtain a melt (step S120), and a step of cooling the melt (step S130).

[0039] Each step will be described below.

[0040] (Step S110) First, the mixed raw materials are mixed.

[0041] The mixed raw material contains a Li source, a B source, an M source, and an O source, where M represents at least one element selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr.

[0042] The mixed raw material is selected from: (i) a combination of three types of compounds, namely (a) a compound containing Li, (b) a compound containing B, and (c) a compound containing M, wherein at least one of (a), (b), and (c) is an oxide; or (ii) a combination of two types of compounds, namely (d) a compound containing Li and B, and (c) a compound containing M, wherein at least one of (d) and (c) is an oxide; or (iii) a combination of two types of compounds, namely (a) a Li compound, and (e) a compound containing B and M, wherein at least one of (a) and (e) is an oxide.

[0043] In the case of the combination (i), the Li-containing compound (a) may be selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride. The B-containing compound (b) may be boric acid (H ３ BO ３ ) or boron trioxide (B ２ O ３ Furthermore, the compound (c) containing M may be selected from the group consisting of oxides, chlorides, sulfates, and carbonates.

[0044] On the other hand, in the case of the combination (ii), the compound (d) containing Li and B is Li ２ B ４ O ７ The compound (c) containing M may also be selected from the group consisting of oxides, chlorides, sulfates, and carbonates.

[0045] Furthermore, in the case of the combination (iii), the compound (a) containing Li may be selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride. Also, the compound (e) containing B and M may be aluminum boride AlB ２ , aluminum borate AlBO ３, silicon boride SiB ４ , aluminum borohydride Al (BH ４ ) ３ The glass may be selected from the group consisting of borosilicate glass, borosilicate glass, and borosilicate glass. Various compositions of borosilicate glass can be used. The borosilicate glass may be, for example, SiO ２ -B ２ O ５ -Al ２ O ３ -Na ２ It may also be of the O type.

[0046] Each compound contained in the mixed raw material may be added in the form of a powder.

[0047] The particle size of each powder is not particularly limited, but the average particle size may be in the range of 1 μm to 50 μm, for example.

[0048] The mixed raw materials are preferably thoroughly mixed by a ball mill treatment or the like.

[0049] (Step S120) Next, the mixed raw materials prepared as described above are heated in the atmosphere to form a melt.

[0050] The heating temperature is not particularly limited as long as it is 930°C or higher, and may be, for example, in the range of 930°C to 1000°C.

[0051] The time for which the material is held at high temperature is not particularly limited, but may be, for example, in the range of 10 minutes to 1 hour. The shorter the holding time, the more efficiently the material for the solid electrolyte can be produced.

[0052] (Step S130) Next, the melt is cooled.

[0053] The cooling method is not particularly limited. For example, the melt may be cooled from a high-temperature state by a method in which the melt is suddenly exposed to an atmospheric room temperature environment (hereinafter referred to as an "air-cooling method"). In the air-cooling method, the average cooling rate v may be in the range of 1°C / sec to 100°C / sec.

[0054] However, it is preferred that the melt be "quenched" at a faster cooling rate.

[0055] In the case of rapid cooling, the average cooling rate from the temperature of the molten material during heating to room temperature is, for example, 100°C / second or more, preferably 200°C / second or more, more preferably 300°C / second or more, and even more preferably 400°C / second or more.

[0056] The average cooling rate v is calculated as follows: Average cooling rate v = T (°C) / t (seconds) Here, T (°C) is the temperature difference between the heating temperature and room temperature, and t (seconds) is the cooling time from the heating temperature to room temperature.

[0057] When the rapid cooling method is adopted, the melt may be cooled by a roll cooling method or a gas atomization method.

[0058] The roll cooling method is a method in which the melt is rapidly cooled by passing it between a set of rotating rolls that have been cooled to a sufficiently low temperature, and the melt is solidified all at once after passing through the rolls. In the roll cooling method, cooling of the melt and pulverization of the product can be carried out simultaneously.

[0059] Gas atomization is a process in which a cooling gas is sprayed at high pressure onto droplets of a melt to break them into particles. In gas atomization, the melt can be cooled and the product can be atomized at the same time.

[0060] On the other hand, in the case of the air-cooling method, when the melt solidifies, a lumpy solid may be generated, so after obtaining the solid, an additional step is performed to crush the solid to form glass cullet or glass powder.

[0061] However, even in the rapid cooling method, a crushing step may be carried out to further reduce the size of the resulting product.

[0062] By the above steps, the first material having the above-mentioned characteristics can be manufactured.

[0063] The first material may have an average particle size in the range of, for example, 0.2 μm to 50 mm.

[0064] (Application Example of Material for Solid Electrolyte According to One Embodiment of the Present Invention) The first material described above can be used, for example, as a framework material when producing a solid electrolyte layer of a secondary battery such as an all-solid-state battery (particularly, an all-solid-state lithium-ion secondary battery).

[0065] For example, the first material may be mixed with water and an electrolyte salt to prepare a solid electrolyte raw material. The electrolyte salt may be Li(FSO ２ ) ２ N may also be used.

[0066] For example, such a solid electrolyte raw material can be formed into a sheet and dried to produce a solid electrolyte sheet.

[0067] Alternatively, the first material can be used as a sheet for an electrode. For example, when the first material is mixed with water, an electrolyte salt, and a positive electrode active material (and a conductive additive), a sheet for a positive electrode can be formed. Similarly, when the first material is mixed with water, an electrolyte salt, and a negative electrode active material (and a conductive additive), a sheet for a negative electrode can be formed.

[0068] It will be apparent to those skilled in the art that there are various other possible applications for the solid electrolyte material according to one embodiment of the present invention.

[0069] Examples of the present invention will be described below. In the following description, Examples 1 to 7 are examples, and Examples 11 to 15 are comparative examples.

[0070] Example 1 A material for a solid electrolyte was produced by the following method.

[0071] First, the mixed raw materials were mixed.

[0072] The mixed raw material was 5g of Li ２ B ４ O ７ powder (average particle size 0.75 μm; manufactured by Kanto Chemical Co., Ltd.) and 0.1 g of Al ２ O ３ The powder (average particle size 2 μm; manufactured by Kanto Chemical Co., Ltd.) was thoroughly mixed in a mortar.

[0073] The material composition calculated from the mixed raw materials is M=Al, x=2.0, y=3.93, and z=0.07 in the above general formula (1).

[0074] Next, this mixed raw material was placed in a platinum crucible, and the platinum crucible was heated at 930°C for 30 minutes to produce a melt. The melt was then subjected to a roll cooling method to obtain cooled glass cullet. The average cooling rate v of the melt was about 435°C / sec.

[0075] The obtained glass cullet (hereinafter referred to as "Sample 1") was glass fragments with an average particle size of about 50 mm.

[0076] The actual composition of Sample 1 was almost the same as the material composition calculated from the mixed raw materials.

[0077] Examples 2 and 3 Glass cullets were produced in the same manner as in Example 1.

[0078] However, in these examples, the Al contained in the mixed raw material ２ O ３ The amount of powder was changed from that in Example 1.

[0079] As a result, glass cullets (hereinafter referred to as "Sample 2" and "Sample 3", respectively) were obtained.

[0080] The composition of Sample 2 corresponds to M=Al, x=2.0, y=3.87, and z=0.13 in the above-mentioned general formula, while the composition of Sample 3 corresponds to M=Al, x=2.0, y=3.67, and z=0.33 in the above-mentioned general formula.

[0081] Example 4 Glass cullet was produced in the same manner as in Example 1.

[0082] However, in this Example 4, Al ２ O ３ Instead of powder, SiO ２ Powder (average particle size 2 μm; manufactured by Kanto Chemical Co., Ltd.) was added.

[0083] As a result, glass cullet (hereinafter referred to as "Sample 4") was obtained.

[0084] The composition of Sample 4 corresponds to M=Si, x=2.0, y=3.85, and z=0.11 in the above general formula (1).

[0085] Example 5 Glass cullet was produced in the same manner as in Example 4.

[0086] However, in Example 5, the SiO contained in the mixed raw material ２ The amount of powder was changed from that in Example 4.

[0087] As a result, glass cullet (hereinafter referred to as "Sample 5") was obtained.

[0088] The composition of Sample 5 corresponds to M=Si, x=2.0, y=3.77, and z=0.17 in the above general formula (1).

[0089] Example 6 Glass cullet was produced in the same manner as in Example 1.

[0090] However, in this Example 6, the mixed raw material contains Li ２ B ４ O ７ powder, Al ２ O ３ powder, and SiO ２ Powder was used.

[0091] As a result, glass cullet (hereinafter referred to as "Sample 6") was obtained.

[0092] The composition of Sample 6 corresponds to M=Al+Si, x=2.0, y=3.92, and z=0.06 in the above general formula (1).

[0093] Example 7 Glass cullet was produced in the same manner as in Example 1.

[0094] However, in Example 7, the melt was cooled not by roll cooling but by removing the platinum crucible heated to 930° C. into the air at room temperature.

[0095] After the molten material solidified, the solidified material was crushed to recover glass cullet (hereinafter referred to as "Sample 7").

[0096] The composition of Sample 7 corresponds to M=Al, x=2.0, y=3.93, and z=0.07 in the above general formula (1).

[0097] Example 11 Glass cullet was produced in the same manner as in Example 1.

[0098] However, in this Example 11, the raw material is Li ２ B ４ O ７ Only powder was used.

[0099] As a result, glass cullet (hereinafter referred to as "Sample 11") was obtained.

[0100] Example 12 Glass cullet was produced in the same manner as in Example 1.

[0101] However, in Example 12, the Al contained in the mixed raw material ２ O ３ The amount of powder was changed from that in Example 1.

[0102] As a result, glass cullet (hereinafter referred to as "Sample 12") was obtained.

[0103] The composition of Sample 12 corresponds to M=Al, x=2.0, y=3.97, and z=0.03 in the above general formula (1).

[0104] Example 13 Glass cullet was produced in the same manner as in Example 4.

[0105] However, in Example 12, the SiO contained in the mixed raw material ２ The amount of powder was changed from that in Example 4.

[0106] As a result, glass cullet (hereinafter referred to as "Sample 13") was obtained.

[0107] The composition of Sample 13 corresponds to M=Si, x=2.0, y=3.93, and z=0.05 in the above general formula (1).

[0108] Example 14 Glass cullet was produced in the same manner as in Example 6.

[0109] However, in Example 14, the Al contained in the mixed raw material ２O ３ Powder and SiO ２ The amount of powder was changed from that in Example 6.

[0110] As a result, glass cullet (hereinafter referred to as "Sample 14") was obtained.

[0111] The composition of Sample 14 corresponds to M=Al+Si, x=2.0, y=3.98, and z=0.03 in the above general formula (1).

[0112] Example 15 Glass cullet was produced in the same manner as in Example 1.

[0113] However, in Example 15, the melting temperature was set to 900°C.

[0114] As a result, glass cullet (hereinafter referred to as "Sample 15") was obtained.

[0115] Table 1 below shows the manufacturing conditions for each sample.

[0116] (Evaluation) The following evaluations were carried out using each sample.

[0117] (X-ray diffraction analysis) Powder X-ray diffraction analysis was performed using each sample. The crystalline / amorphous nature of the sample was determined based on the presence or absence of diffraction peaks derived from crystals in the analysis results. That is, if a diffraction peak appeared in the X-ray diffraction chart, the sample was determined to be crystalline, and if no diffraction peak was observed, the sample was determined to be amorphous.

[0118] The "crystal structure" column in Table 1 above shows the crystalline state of each sample.

[0119] 2 and 3 show X-ray diffraction charts of Sample 1 and Sample 11, respectively.

[0120] The results showed that the glasslets obtained in Samples 11 to 15 were crystalline, while the glasslets obtained in Samples 1 to 7 were amorphous.

[0121] From the above results, it was confirmed that in Samples 1 to 7, amorphous materials applicable to solid electrolytes could be produced relatively easily.

[0122] (Aspects of the Invention) The present invention may have the following aspects.

[0123] (Aspect 1) A method for producing a material for a solid electrolyte, comprising: (1) preparing a mixed raw material, the mixed raw material having a lithium (Li) source, a boron (B) source, an M source, and an oxygen (O) source, wherein M is at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, the mixed raw material being: (i) a combination of three types of compounds, namely, a compound (a) containing Li, a compound (b) containing B, and a compound (c) containing M, wherein at least one of (a), (b), and (c) is an oxide, or (ii) a combination of two types of compounds, namely, a compound (d) containing Li and B, and a compound (c) containing M, wherein at least one of (d) and (c) is an oxide, or (iii) a combination of two types of compounds, namely, a Li compound (a) and a compound (e) containing B and M, wherein at least one of (a) and (e) is an oxide, (2) a step of heating the mixed raw material to 930°C or higher to obtain a melt; and (3) a step of cooling the melt to obtain an amorphous material, wherein the amorphous material is selected from the group consisting of a compound represented by the following general formula: ｘ B ｙ M ｚ O ７ (1) where 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4.

[0124] (Embodiment 2) The method according to embodiment 1, wherein in the step (3), the melt is rapidly cooled.

[0125] (Embodiment 3) The method according to embodiment 1, wherein the step (3) comprises a step of roll-cooling or gas-atomizing the melt.

[0126] (Aspect 4) The method according to any one of Aspects 1 to 3, wherein in the step (3), the amorphous material containing glass cullet or glass powder is directly produced by cooling the melt.

[0127] (Aspect 5) The method according to aspect 1, wherein the step (3) comprises: cooling the melt to obtain a solidified product, and then pulverizing the solidified product to obtain an amorphous material containing glass cullet or glass powder.

[0128] (Aspect 6) The method according to any one of aspects 1 to 5, wherein M is Si and / or Al.

[0129] (Aspect 7) The method according to any one of aspects 1 to 5, wherein in the general formula (1), M is Al and z>0.07.

[0130] (Embodiment 8) The method according to any one of embodiments 1 to 5, wherein in the general formula (1), M is Si and z>0.11.

[0131] (Aspect 9) The method according to any one of Aspects 1 to 8, wherein the Li-containing compound (a) is selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride; the B-containing compound (b) is boric acid or boron trioxide; and the M-containing compound (c) is selected from the group consisting of oxides, chlorides, sulfates, and carbonates.

[0132] (Aspect 10) The compound (d) containing Li and B is Li ２ B ４ O ７ Aspect 9. The method of any one of aspects 1 to 8, wherein the compound (c) comprising M is selected from the group consisting of oxides, chlorides, sulfates, and carbonates.

[0133] (Aspect 11) The compound (a) containing Li is selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride, and the compound (e) containing B and M is aluminum borohydride Al(BH ４ ) ３9. The method of any one of aspects 1 to 8, wherein the glass is selected from the group consisting of: and borosilicate glass.

[0134] (Aspect 12) A material for a solid electrolyte, which is amorphous and has the following general formula: Li ｘ B ｙ M ｚ O ７ (1) A material for a solid electrolyte, wherein M includes at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, and 2≦x≦3, y>0, z≧0.06, and 3≦y+z≦4, and wherein M is contained in a glass structure.

[0135] (Aspect 13) The material for a solid electrolyte according to aspect 12, wherein M is Si and / or Al.

[0136] (Aspect 14) The material for a solid electrolyte according to aspect 12, wherein in the general formula (1), M is Al and z>0.07.

[0137] (Aspect 15) The material for a solid electrolyte according to aspect 12, wherein in the general formula (1), M is Si and z>0.11.

[0138] This application claims priority based on Japanese Patent Application No. 2023-220301, filed on December 27, 2023, the entire contents of which are incorporated herein by reference.

Claims

1. A method for manufacturing a material for a solid electrolyte, comprising: (1) a step of preparing a mixed raw material, wherein the mixed raw material has a lithium (Li) source, a boron (B) source, an M source, and an oxygen (O) source, where M is at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, and the mixed raw material is (i) a combination of three types of compounds, namely a compound (a) containing Li, a compound (b) containing B, and a compound (c) containing M, where at least one of (a), (b), and (c) is an oxide, or (ii) a combination of two types of compounds, namely a compound (d) containing Li and B, and a compound (c) containing M, where at least one of (d) and (c) is an oxide, or (iii) a combination of two types of compounds, namely a Li compound (a), and a compound (e) containing B and M, where at least one of (a) and (e) is an oxide, selected from the above, and (2) a step of heating the mixed raw material to 930 °C or higher to obtain a melt, and (3) a step of cooling the melt to obtain an amorphous material, where the amorphous material is represented by the following general formula: Li ｘ B ｙ M ｚ O ７ (1) where 2 ≤ x ≤ 3, y > 0, z ≥ 0.06, and 3 ≤ y + z ≤ 4, and having the above steps.

2. The method according to claim 1, wherein in the step (3), the melt is rapidly cooled.

3. The method according to claim 1, wherein the step (3) has a step of roll-cooling or gas atomizing the melt.

4. The method according to claim 1, wherein in the step (3), the amorphous material containing glass cullets or glass powder is directly produced by cooling the melt.

5. The method according to claim 1, wherein the step (3) has a step of cooling the melt to obtain a solidified product and then pulverizing the solidified product to obtain an amorphous material containing glass cullets or glass powder.

6. The method according to claim 1, wherein M is Si and / or Al.

7. The method according to claim 1, wherein in the general formula (1), M is Al and z > 0.

07.

8. The method according to claim 1, wherein in the general formula (1), M is Si and z > 0.

11.

9. The compound (a) containing Li is selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride; the compound (b) containing B is boric acid or boron trioxide; and the compound (c) containing M is selected from the group consisting of oxides, chlorides, sulfates, and carbonates. The method according to claim 1.

10. The compound (d) containing Li and B is Li ２ B ４ O ７ and the compound (c) containing M is selected from the group consisting of oxides, chlorides, sulfates, and carbonates. The method according to claim 1.

11. The compound (a) containing Li is selected from the group consisting of lithium carbonate, lithium oxide, lithium sulfate, lithium nitrate, and lithium chloride, and the compound (e) containing B and M is selected from the group consisting of aluminum borohydride Al(BH ４ ) ３ and borosilicate glass. The method according to claim 1 12. A material for a solid electrolyte, which is amorphous and has the following general formula: Li ｘ B ｙ M ｚ O ７ (1) wherein M contains at least one selected from the group consisting of P, As, Si, Ge, Sb, Ti, Sn, Al, and Zr, 2 ≦ x ≦ 3, y > 0, z ≧ 0.06, and 3 ≦ y + z ≦ 4, and the M is contained in a glass structure, a material for a solid electrolyte.

13. The material for a solid electrolyte according to claim 12, wherein M is Si and / or Al.

14. The material for a solid electrolyte according to claim 12, wherein in the general formula (1), M is Al and z > 0.

07.

15. The material for a solid electrolyte according to claim 12, wherein in the general formula (1), M is Si and z > 0.11.

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