Solid electrolyte material and battery using the same

Abstract

The solid electrolyte material according to the present disclosure comprises, in essence, Li, M1, M2, O, and X. Here, M1 represents at least one element selected from the group consisting of Ta and Nb, M2 represents at least one element selected from the group consisting of Zr, Y, and La, and X represents at least one element selected from the group consisting of F, Cl, and Br.

Description

[Technical Field]

[0001] The present disclosure relates to a solid electrolyte material and a battery using the same. [Background technology]

[0002] Patent Document 1 discloses an all-solid-state battery using a sulfide solid electrolyte material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-129312 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a new, highly useful solid electrolyte material. [Means for solving the problem]

[0005] The solid electrolyte material of the present disclosure consists essentially of Li, M1, M2, O, and X, where M1 is at least one selected from the group consisting of Ta and Nb, M2 is at least one selected from the group consisting of Zr, Y, and La, and X is at least one selected from F, Cl, and Br. [Effects of the Invention]

[0006] The present disclosure provides a new, highly useful solid electrolyte material. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment. [Figure 2] FIG. 2 shows a cross-sectional view of an electrode material 1100 according to a second embodiment. [Figure 3] FIG. 3 shows a schematic diagram of a pressing die 300 used to evaluate the ionic conductivity of a solid electrolyte material. [Figure 4A] FIG. 4A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 1, 3, 5, 7, 9, and 11. [Figure 4B] FIG. 4B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 2, 4, 6, 8, 10, and 12. [Figure 5A] FIG. 5A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 13 to 16. [Figure 5B] FIG. 5B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 17 to 19. [Figure 6A] FIG. 6A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 20 to 23. [Figure 6B] FIG. 6B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 24 to 27. [Figure 7] FIG. 7 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 28 to 31. [Figure 8] FIG. 8 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Comparative Examples 1 and 2. [Figure 9] FIG. 9 is a graph showing the initial discharge characteristics of the battery according to Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0008] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The present disclosure is not limited to the following embodiments.

[0009] (First embodiment) The solid electrolyte material according to the first embodiment is essentially composed of Li, M1, M2, O, and X. Here, M1 is at least one selected from the group consisting of Ta and Nb, M2 is at least one selected from the group consisting of Zr, Y, and La, and X is at least one selected from F, Cl, and Br.

[0010] Here, "the solid electrolyte material according to the first embodiment is substantially composed of Li, M1, M2, O, and X" means that the ratio (i.e., molar fraction) of the total amount of substance of Li, M1, M2, O, and X to the total amount of substance of all elements constituting the solid electrolyte material according to the first embodiment is 90% or more. As an example, this ratio may be 95% or more. The solid electrolyte material according to the first embodiment may be composed only of Li, M1, M2, O, and X.

[0011] The solid electrolyte material according to the first embodiment can have, for example, a practical lithium ion conductivity, for example, a high lithium ion conductivity. Here, the high lithium ion conductivity is, for example, 1×10 -3 That is, the solid electrolyte material according to the first embodiment has a conductivity of, for example, 1×10 -3 It may have an ionic conductivity of mS / cm or more.

[0012] The solid electrolyte material according to the first embodiment can be used to obtain a battery having excellent charge / discharge characteristics. An example of such a battery is an all-solid-state battery. The all-solid-state battery may be a primary battery or a secondary battery.

[0013] The solid electrolyte material according to the first embodiment can maintain high lithium ion conductivity in the expected temperature range of the battery. Therefore, the battery using the solid electrolyte material according to the first embodiment can operate stably even in an environment with temperature changes. The temperature range of the battery is, for example, from -30°C to 80°C.

[0014] It is desirable that the solid electrolyte material according to the first embodiment is substantially free of sulfur. The term "substantially free of sulfur" in the solid electrolyte material according to the first embodiment means that the solid electrolyte material does not contain sulfur as a constituent element, except for sulfur inevitably mixed in as an impurity. In this case, the amount of sulfur mixed in the solid electrolyte material as an impurity is, for example, 1 mol % or less. It is preferable that the solid electrolyte material according to the first embodiment is free of sulfur. A sulfur-free solid electrolyte material is excellent in safety because it does not generate hydrogen sulfide even when exposed to the atmosphere. The sulfide solid electrolyte material disclosed in Patent Document 1 may generate hydrogen sulfide when exposed to the atmosphere.

[0015] The solid electrolyte material according to the first embodiment may contain a first crystalline phase having a diffraction peak in a range of diffraction angles 2θ of 11.08° or more and 14.12° or less (hereinafter referred to as the "first range") in an X-ray diffraction pattern.

[0016] The first crystalline phase has high lithium ion conductivity. The solid electrolyte material according to the first embodiment contains the first crystalline phase, which makes it easier to form paths for lithium ions to diffuse. As a result, the solid electrolyte material according to the first embodiment has high lithium ion conductivity.

[0017] Diffraction peaks in an X-ray diffraction pattern will hereinafter be simply referred to as "peaks".

[0018] The X-ray diffraction pattern of the solid electrolyte material according to the first embodiment can be obtained by X-ray diffraction measurement by the θ-2θ method using Cu-Kα radiation (wavelengths of 1.5405 Å and 1.5444 Å, ie, wavelengths of 0.15405 nm and 0.15444 nm).

[0019] The peak angle is the angle at which the maximum intensity of the mountain-shaped part where the SN ratio is 3 or more and the half-width is 10° or less. The half-width is the maximum intensity of the peak. MAX When the intensity is I MAXThe signal-to-noise ratio (SN ratio) is the ratio of the signal S to the background noise N.

[0020] To enhance the ionic conductivity of the solid electrolyte material, X may be at least one selected from the group consisting of Cl and Br.

[0021] In order to increase the ionic conductivity of the solid electrolyte material, the ratio of the amount of substance M2 to the sum of the amounts of substances M1 and M2 may be greater than 0% and less than or equal to 60%. The ratio of the amount of substance M2 to the sum of the amounts of substances M1 and M2 is calculated by the formula: {(amount of substance M2) / (amount of substance M1+amount of substance M2)}×100. Hereinafter, the ratio of the amount of substance M2 to the sum of the amounts of substances M1 and M2 is also referred to as the "M2 / (M1+M2) molar ratio."

[0022] To enhance the ionic conductivity of the solid electrolyte material, the M2 / (M1+M2) molar ratio may be 5% or more and 50% or less.

[0023] To enhance the ionic conductivity of the solid electrolyte material, the M2 / (M1+M2) molar ratio may be 10% or more and 50% or less.

[0024] In order to enhance the electrochemical stability of the solid electrolyte material, X may contain F. From the viewpoint of ionic conductivity, the ratio of the amount of F to the amount of X may be 0% or more and 65% or less. The ratio of the amount of F to the amount of X is also called the "F / X molar ratio." The F / X molar ratio is calculated by the formula: {(amount of F) / (total amount of F, Cl, and Br)}×100.

[0025] To enhance the electrochemical stability of the solid electrolyte material, the F / X molar ratio may be 0% or more and 50% or less.

[0026] To further enhance the electrochemical stability of the solid electrolyte material, the F / X molar ratio may be 0% or more and 25% or less.

[0027] To further enhance the electrochemical stability of the solid electrolyte material, the F / X molar ratio may be 0% or more and 5% or less.

[0028] In order to increase the ionic conductivity of the solid electrolyte material, M2 may be Zr, which allows the solid electrolyte material to have not only high ionic conductivity but also high electrochemical stability.

[0029] The shape of the solid electrolyte material according to the first embodiment is not limited. Examples of the shape include a needle shape, a sphere shape, and an oval sphere shape. The solid electrolyte material according to the first embodiment may be in the form of particles. The solid electrolyte material according to the first embodiment may be formed into a pellet or plate shape.

[0030] When the solid electrolyte material according to the first embodiment is particulate (e.g., spherical), the solid electrolyte material may have a median diameter of 0.1 μm or more and 100 μm or less, or may have a median diameter of 0.5 μm or more and 10 μm or less. This allows the solid electrolyte material according to the first embodiment and other materials to be dispersed well. The median particle diameter refers to the particle size (d50) corresponding to 50% cumulative volume in the volume-based particle size distribution. The volume-based particle size distribution can be measured using a laser diffraction measurement device or an image analysis device.

[0031] <Method of manufacturing solid electrolyte material> The solid electrolyte material according to the first embodiment can be produced by the following method.

[0032] Raw material powders are prepared and mixed to have a desired composition, examples of which include oxides, hydroxides, halides, or oxyhalides.

[0033] As an example, if the solid electrolyte material is composed of Li, Ta, Zr, O, and Cl, and the M2 / (M1+M2) molar ratio and F / X molar ratio during raw material mixing are 10% and 0%, respectively, i.e., M1 is Ta, M2 is Zr, and X is Cl, and the M2 / (M1+M2) molar ratio and F / X molar ratio during raw material mixing are 10% and 0%, respectively, Li2O2, TaCl5, and ZrCl4 are mixed as raw material powders in a Li2O2:TaCl5:ZrCl4 molar ratio of 1:1.8:0.2. M1, M2, and X are determined by the selection of raw material powders. The M2 / (M1+M2) molar ratio and F / X molar ratio are determined by the selection of the raw material powder mixing ratio. The raw material powders may be mixed in a pre-adjusted molar ratio to offset compositional changes that may occur during the synthesis process.

[0034] A mixture of raw material powders is reacted mechanochemically in a mixing device such as a planetary ball mill to obtain a reactant. This method is often called mechanochemical milling. The reactant may be calcined in a vacuum or in an inert atmosphere. Alternatively, the mixture may be calcined in a vacuum or in an inert gas atmosphere to obtain a reactant. These methods produce the solid electrolyte material according to the first embodiment. The inert atmosphere is, for example, an argon atmosphere or a nitrogen atmosphere.

[0035] By selecting the raw material powders, the mixing ratio of the raw material powders, and the reaction conditions, the peak position of the solid electrolyte material according to the first embodiment, that is, the structure of the crystalline phase, can be adjusted to the desired one.

[0036] The composition of the solid electrolyte material can be determined, for example, by inductively coupled plasma atomic emission spectroscopy or ion chromatography. For example, the compositions of Li, M1, and M2 can be determined by inductively coupled plasma atomic emission spectroscopy, and the composition of X can be determined by ion chromatography.

[0037] (Second embodiment) The second embodiment will be described below, and the matters described in the first embodiment will be omitted as appropriate.

[0038] The battery according to the second embodiment includes a positive electrode, an electrolyte layer, and a negative electrode. The electrolyte layer is disposed between the positive electrode and the negative electrode. At least one selected from the group consisting of the positive electrode, the electrolyte layer, and the negative electrode contains the solid electrolyte material according to the first embodiment.

[0039] The battery according to the second embodiment has excellent charge / discharge characteristics because it contains the solid electrolyte material according to the first embodiment.

[0040] FIG. 1 shows a cross-sectional view of a battery 1000 according to a second embodiment.

[0041] The battery 1000 includes a positive electrode 201, an electrolyte layer 202, and a negative electrode 203. The electrolyte layer 202 is disposed between the positive electrode 201 and the negative electrode 203.

[0042] The positive electrode 201 contains positive electrode active material particles 204 and solid electrolyte particles 100 .

[0043] The electrolyte layer 202 contains an electrolyte material, such as a solid electrolyte material.

[0044] The negative electrode 203 contains negative electrode active material particles 205 and solid electrolyte particles 100 .

[0045] The solid electrolyte particle 100 is a particle containing the solid electrolyte material according to the first embodiment. The solid electrolyte particle 100 may be a particle containing the solid electrolyte material according to the first embodiment as a main component. Particles containing the solid electrolyte material according to the first embodiment as a main component refer to particles in which the component contained in the largest amount in terms of molar ratio is the solid electrolyte material according to the first embodiment. The solid electrolyte particle 100 may be a particle made of the solid electrolyte material according to the first embodiment.

[0046] The positive electrode 201 contains a material capable of absorbing and releasing metal ions such as lithium ions. The material is, for example, a positive electrode active material (for example, positive electrode active material particles 204).

[0047] Examples of the positive electrode active material include lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, or transition metal oxynitrides. Examples of the lithium-containing transition metal oxides include Li(Ni,Co,Al)O2, Li(Ni,Co,Mn)O2, or LiCoO2. From the viewpoints of battery cost and safety, lithium phosphate may be used as the positive electrode active material.

[0048] In the present disclosure, "(A,B,C)" means "at least one selected from the group consisting of A, B, and C".

[0049] The positive electrode 201 may contain not only the solid electrolyte material according to the first embodiment but also a transition metal oxyfluoride as the positive electrode active material. Even if the solid electrolyte material according to the first embodiment is fluorinated with a transition metal fluoride, it is difficult to form a resistance layer. As a result, the battery has high charge-discharge efficiency.

[0050] The transition metal oxyfluoride contains oxygen and fluorine. As an example, the transition metal oxyfluoride may be a compound represented by the compositional formula Li p Me q O m F n Here, Me is at least one selected from the group consisting of Mn, Co, Ni, Fe, Al, Cu, V, Nb, Mo, Ti, Cr, Zr, Zn, Na, K, Ca, Mg, Pt, Au, Ag, Ru, W, B, Si, and P, and the following mathematical formulas: 0.5 ≦ p ≦ 1.5, 0.5 ≦ q ≦ 1.0, 1 ≦ m < 2, and 0 < n ≦ 1 are satisfied. An example of such a transition metal oxyfluoride is Li 1.05 (Ni 0.35 Co 0.35 Mn 0.3 ) 0.95 O 1.9 F 0.1 is.

[0051] The positive electrode active material particles 204 may have a median diameter of 0.1 μm or more and 100 μm or less. When the positive electrode active material particles 204 have a median diameter of 0.1 μm or more, the positive electrode active material particles 204 and the solid electrolyte particles 100 can be well dispersed in the positive electrode 201. This improves the charge / discharge characteristics of the battery. When the positive electrode active material particles 204 have a median diameter of 100 μm or less, the lithium diffusion rate within the positive electrode active material particles 204 improves. This allows the battery to operate at high power.

[0052] The positive electrode active material particles 204 may have a larger median diameter than the solid electrolyte particles 100. This allows the positive electrode active material particles 204 and the solid electrolyte particles 100 to be dispersed well.

[0053] In order to increase the energy density and output of the battery, in the positive electrode 201, the ratio of the volume of the positive electrode active material particles 204 to the sum of the volume of the positive electrode active material particles 204 and the volume of the solid electrolyte particles 100 may be 0.30 or more and 0.95 or less.

[0054] FIG. 2 shows a cross-sectional view of an electrode material 1100 according to a second embodiment. The electrode material 1100 is included in, for example, a positive electrode 201. A coating layer 216 may be formed on the surface of the electrode active material particles 206 to prevent the electrode active material particles 206 (i.e., the positive electrode active material) from reacting with the solid electrolyte particles 100. This can suppress an increase in the reaction overvoltage of the battery. Examples of coating materials included in the coating layer 216 include a sulfide solid electrolyte, an oxide solid electrolyte, or a halide solid electrolyte.

[0055] When the solid electrolyte particle 100 is a sulfide solid electrolyte, the coating material may be the solid electrolyte material according to the first embodiment. The solid electrolyte material according to the first embodiment is less susceptible to oxidation than the sulfide solid electrolyte, and therefore can suppress an increase in the reaction overvoltage of the battery.

[0056] To increase the energy density and power output of the battery, the positive electrode 201 may have a thickness of 10 μm or more and 500 μm or less.

[0057] The electrolyte layer 202 contains an electrolyte material. The electrolyte material is, for example, a solid electrolyte material. The electrolyte layer 202 may be a solid electrolyte layer.

[0058] The electrolyte layer 202 may contain the solid electrolyte material according to the first embodiment, or may consist solely of the solid electrolyte material according to the first embodiment.

[0059] The solid electrolyte material contained in the electrolyte layer 202 may be composed solely of a solid electrolyte material different from the solid electrolyte material according to the first embodiment. Examples of the solid electrolyte material different from the solid electrolyte material according to the first embodiment include Li2MgX'4, Li2FeX'4, Li(Al,Ga,In)X'4, Li3(Al,Ga,In)X'6, or LiI, where X' is at least one selected from the group consisting of F, Cl, Br, and I.

[0060] Hereinafter, the solid electrolyte material according to the first embodiment will be referred to as a first solid electrolyte material, and a solid electrolyte material different from the solid electrolyte material according to the first embodiment will be referred to as a second solid electrolyte material.

[0061] The electrolyte layer 202 may contain not only the first solid electrolyte material but also the second solid electrolyte material. The first solid electrolyte material and the second solid electrolyte material may be uniformly dispersed. A layer made of the first solid electrolyte material and a layer made of the second solid electrolyte material may be stacked along the stacking direction of the battery 1000.

[0062] The electrolyte layer 202 may have a thickness of 1 μm or more and 100 μm or less. When the electrolyte layer 202 has a thickness of 1 μm or more, the positive electrode 201 and the negative electrode 203 are less likely to short-circuit. When the electrolyte layer 202 has a thickness of 100 μm or less, the battery can operate at high power.

[0063] Another electrolyte layer may be further provided between the electrolyte layer 202 and the negative electrode 203. That is, a second electrolyte layer may be further provided between the electrolyte layer 202 and the negative electrode 203. For example, when the electrolyte layer 202 contains a first solid electrolyte material, the second electrolyte layer may be composed of another solid electrolyte material that is electrochemically more stable than the first solid electrolyte material. Specifically, the reduction potential of the solid electrolyte material constituting the second electrolyte layer may be lower than the reduction potential of the first solid electrolyte material. This allows the first solid electrolyte material to be used without being reduced, and the high ionic conductivity of the first solid electrolyte material can be more stably maintained. As a result, the charge / discharge efficiency of the battery can be improved.

[0064] The negative electrode 203 contains a material capable of absorbing and releasing metal ions (for example, lithium ions). The material is, for example, a negative electrode active material (for example, negative electrode active material particles 205).

[0065] Examples of the negative electrode active material include a metal material, a carbon material, an oxide, a nitride, a tin compound, or a silicon compound. The metal material may be a simple metal or an alloy. An example of the metal material is lithium metal or a lithium alloy. Examples of the carbon material are natural graphite, coke, partially graphitized carbon, carbon fiber, spherical carbon, artificial graphite, or amorphous carbon. From the viewpoint of capacity density, suitable examples of the negative electrode active material are silicon (Si), tin (Sn), a silicon compound, or a tin compound.

[0066] The negative electrode active material may be selected based on the reduction resistance of the solid electrolyte material contained in the negative electrode 203. When the negative electrode 203 contains a first solid electrolyte material, a material capable of absorbing and releasing lithium ions at 0.27 V or higher relative to lithium may be used as the negative electrode active material. If the negative electrode active material is such a material, reduction of the first solid electrolyte material contained in the negative electrode 203 can be suppressed. As a result, the battery has high charge / discharge efficiency. Examples of such negative electrode active materials include titanium oxide, indium metal, or lithium alloy. An example of titanium oxide is Li4Ti5O 12 , LiTi2O4, or TiO2.

[0067] The negative electrode active material particles 205 may have a median diameter of 0.1 μm or more and 100 μm or less. When the negative electrode active material particles 205 have a median diameter of 0.1 μm or more, the negative electrode active material particles 205 and the solid electrolyte particles 100 can be well dispersed in the negative electrode 203. This improves the charge / discharge characteristics of the battery. When the negative electrode active material particles 205 have a median diameter of 100 μm or less, the lithium diffusion rate within the negative electrode active material particles 205 improves. This allows the battery to operate at high power.

[0068] The negative electrode active material particles 205 may have a larger median diameter than the solid electrolyte particles 100. This allows the negative electrode active material particles 205 and the solid electrolyte particles 100 to be dispersed well.

[0069] In order to increase the energy density and output of the battery, in the negative electrode 203, the ratio of the volume of the negative electrode active material particles 205 to the sum of the volume of the negative electrode active material particles 205 and the volume of the solid electrolyte particles 100 may be 0.30 or more and 0.95 or less.

[0070] The electrode material 1100 shown in FIG. 2 is included in, for example, the negative electrode 203. A coating layer 216 may be formed on the surface of the electrode active material particles 206 to prevent the electrode active material particles 206 (i.e., the negative electrode active material) from reacting with the solid electrolyte particles 100. This allows the battery to have high charge / discharge efficiency. Examples of coating materials included in the coating layer 216 include a sulfide solid electrolyte, an oxide solid electrolyte, a polymer solid electrolyte, or a halide solid electrolyte.

[0071] When the solid electrolyte particles 100 are the first solid electrolyte material, the coating material may include a sulfide solid electrolyte, an oxide solid electrolyte, or a polymer solid electrolyte. An example of a sulfide solid electrolyte is Li2S-P2S5. An example of an oxide solid electrolyte is trilithium phosphate. An example of a polymer solid electrolyte is a composite compound of polyethylene oxide and a lithium salt. An example of such a polymer solid electrolyte is lithium bis(trifluoromethanesulfonyl)imide.

[0072] To increase the energy density and power output of the battery, the negative electrode 203 may have a thickness of 10 μm or more and 500 μm or less.

[0073] At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a second solid electrolyte material for the purpose of increasing ion conductivity. Examples of the second solid electrolyte material include a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, or an organic polymer solid electrolyte.

[0074] In this disclosure, a "sulfide solid electrolyte" refers to a solid electrolyte containing sulfur. An "oxide solid electrolyte" refers to a solid electrolyte containing oxygen. The oxide solid electrolyte may contain anions other than oxygen (excluding sulfur anions and halogen anions). A "halide solid electrolyte" refers to a solid electrolyte that contains a halogen element and is substantially free of sulfur. The halide solid electrolyte may contain not only a halogen element but also oxygen.

[0075] Examples of sulfide solid electrolytes are Li2S-P2S5, Li2S-SiS2, Li2S-B2S3, Li2S-GeS2, Li 3.25 Ge 0.25 P 0.75 S4, or Li 10 GeP2S 12 is.

[0076] Examples of oxide solid electrolytes include: (i) NASICON-type solid electrolytes such as LiTi2(PO4)3 or its elemental substitutes; (ii) Perovskite-type solid electrolytes such as (LaLi)TiO3; (iii) Li 14 ZnGeO 16 LISICON-type solid electrolytes such as Li4SiO4, LiGeO4 or elemental substitutions thereof; (iv) Li7La3Zr2O 12or a garnet-type solid electrolyte such as an elemental substitution product thereof, or (v) Li3PO4 or its N-substituted derivatives is.

[0077] An example of a halide solid electrolyte is Li a Me' b Y c The compound is represented by Z6, where the formula: a+mb+3c=6, and c>0 is satisfied. Me' is at least one selected from the group consisting of metal elements and metalloid elements other than Li and Y. Z is at least one selected from the group consisting of F, Cl, Br, and I. The value of m represents the valence of Me'.

[0078] "Semi-metallic elements" are B, Si, Ge, As, Sb, and Te.

[0079] "Metallic elements" are all elements in Groups 1 to 12 of the periodic table (excluding hydrogen) and all elements in Groups 13 to 16 of the periodic table (excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se).

[0080] To enhance the ionic conductivity of the halide solid electrolyte, Me′ may be at least one selected from the group consisting of Mg, Ca, Sr, Ba, Zn, Sc, Al, Ga, Bi, Zr, Hf, Ti, Sn, Ta, and Nb.

[0081] Examples of halide solid electrolytes are Li3YCl6 or Li3YBr6.

[0082] When the electrolyte layer 202 contains the first solid electrolyte material, the negative electrode 203 may contain a sulfide solid electrolyte. This allows the sulfide solid electrolyte, which is electrochemically stable with respect to the negative electrode active material, to prevent the first solid electrolyte material and the negative electrode active material from coming into contact with each other. As a result, the battery has low internal resistance.

[0083] Examples of organic polymer solid electrolytes include compounds of polymer compounds and lithium salts. The polymer compounds may have an ethylene oxide structure. Polymer compounds having an ethylene oxide structure can contain a large amount of lithium salt, and therefore have higher ionic conductivity.

[0084] Examples of lithium salts include LiPF, LiBF, LiSbF, LiAsF, LiSOCF, LiN(SOCF), LiN(SOCF) , LiN(SOCF)(SOCF), or LiC(SOCF). One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used.

[0085] At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a non-aqueous electrolyte, a gel electrolyte, or an ionic liquid in order to facilitate the exchange of lithium ions and improve the output characteristics of the battery.

[0086] The nonaqueous electrolyte contains a nonaqueous solvent and a lithium salt dissolved in the nonaqueous solvent. Examples of the nonaqueous solvent include a cyclic carbonate ester solvent, a chain carbonate ester solvent, a cyclic ether solvent, a chain ether solvent, a cyclic ester solvent, a chain ester solvent, or a fluorine solvent. Examples of the cyclic carbonate ester solvent are ethylene carbonate, propylene carbonate, or butylene carbonate. Examples of the chain carbonate ester solvent are dimethyl carbonate, ethyl methyl carbonate, or diethyl carbonate. Examples of the cyclic ether solvent are tetrahydrofuran, 1,4-dioxane, or 1,3-dioxolane. Examples of the chain ether solvent are 1,2-dimethoxyethane or 1,2-diethoxyethane. An example of the cyclic ester solvent is γ-butyrolactone. An example of the chain ester solvent is methyl acetate. Examples of fluorine-containing solvents include fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, and fluorodimethylene carbonate. One non-aqueous solvent selected from these may be used alone. Alternatively, a mixture of two or more non-aqueous solvents selected from these may be used.

[0087] Examples of lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), and LiC(SO2CF3)3. One lithium salt selected from these may be used alone. Alternatively, a mixture of two or more lithium salts selected from these may be used. The concentration of the lithium salt is, for example, in the range of 0.5 mol / L to 2 mol / L.

[0088] The gel electrolyte may be a polymer material impregnated with a non-aqueous electrolyte, such as polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, or a polymer having an ethylene oxide bond.

[0089] Examples of cations contained in ionic liquids are: (i) aliphatic chain quaternary salts such as tetraalkylammonium or tetraalkylphosphonium; (ii) aliphatic cyclic ammoniums such as pyrrolidiniums, morpholiniums, imidazoliniums, tetrahydropyrimidiniums, piperaziniums, or piperidiniums, or (iii) nitrogen-containing heterocyclic aromatic cations such as pyridiniums or imidazoliums is.

[0090] An example of an anion found in ionic liquids is PF6 - , BF4 - , SbF6 - , AsF6 - , SO3CF3 - , N(SO2CF3)2 - , N(SO2C2F5)2 - , N(SO2CF3)(SO2C4F9) - , or C(SO2CF3)3 - is.

[0091] The ionic liquid may contain a lithium salt.

[0092] At least one selected from the group consisting of the positive electrode 201, the electrolyte layer 202, and the negative electrode 203 may contain a binder to enhance adhesion between particles.

[0093] Examples of binders include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polymethyl ester of acrylic acid, polyethyl ester of acrylic acid, polyhexyl ester of acrylic acid, polymethacrylic acid, polymethyl ester of methacrylic acid, polyethyl ester of methacrylic acid, polyhexyl ester of methacrylic acid, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene-butadiene rubber, and carboxymethyl cellulose. Copolymers may also be used as binders. Examples of such binders include copolymers of two or more materials selected from the group consisting of tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride, chlorotrifluoroethylene, ethylene, propylene, pentafluoropropylene, fluoromethyl vinyl ether, acrylic acid, and hexadiene. Mixtures of two or more of the above materials may also be used.

[0094] At least one selected from the group consisting of the positive electrode 201 and the negative electrode 203 may contain a conductive additive to enhance electronic conductivity.

[0095] Examples of the conductive additive include: (i) graphites such as natural or synthetic graphite; (ii) carbon blacks such as acetylene black or ketjen black; (iii) conductive fibers such as carbon or metal fibers; (iv) fluorocarbons, (v) metal powders such as aluminum; (vi) conductive whiskers such as zinc oxide or potassium titanate; (vii) a conductive metal oxide, such as titanium oxide, or (viii) Conductive polymer compounds such as polyaniline, polypyrrole, or polythiophene To reduce costs, the above-mentioned conductive additive (i) or (ii) may be used.

[0096] Examples of the shape of the battery according to the second embodiment include a coin type, a cylindrical type, a square type, a sheet type, a button type, a flat type, and a laminate type.

[0097] The battery according to the second embodiment may be manufactured, for example, by preparing a material for forming a positive electrode, a material for forming an electrolyte layer, and a material for forming a negative electrode, and by using a known method to fabricate a laminate in which the positive electrode, the electrolyte layer, and the negative electrode are arranged in this order. [Example]

[0098] Hereinafter, the present disclosure will be described in more detail with reference to examples.

[0099] Example 1 [Preparation of solid electrolyte materials] In a dry atmosphere with a dew point of -30°C or less (hereinafter referred to as "dry atmosphere"), raw material powders of Li2O2, TaCl5, and ZrCl4 were prepared in a molar ratio of Li2O2:TaCl5:ZrCl4 of 1:1.8:0.2. These materials were ground and mixed in a mortar to obtain a mixture. The obtained mixture was milled at 600 rpm for 24 hours using a planetary ball mill (Fritsch, P-7 model). In this way, a powder of the solid electrolyte material according to Example 1 was obtained.

[0100] [Evaluation of ionic conductivity] FIG. 3 shows a schematic diagram of a pressing die 300 used to evaluate the ionic conductivity of the solid electrolyte material.

[0101] The pressure molding die 300 had an upper punch 301, a frame 302, and a lower punch 303. The frame 302 was made of insulating polycarbonate. The upper punch 301 and the lower punch 303 were both made of electronically conductive stainless steel.

[0102] Using the pressure molding die 300 shown in FIG. 3, the ionic conductivity of the solid electrolyte material of Example 1 was measured by the following method.

[0103] In a dry atmosphere, the powder of the solid electrolyte material according to Example 1 was filled into a pressure molding die 300. Inside the pressure molding die 300, a pressure of 300 MPa was applied to the solid electrolyte material according to Example 1 (i.e., powder 101 of the solid electrolyte material in FIG. 3 ) using an upper punch 301 and a lower punch 303.

[0104] While the pressure was still applied, the upper punch 301 and the lower punch 303 were connected to a potentiostat (VersaSTAT4, manufactured by Princeton Applied Research) equipped with a frequency response analyzer. The upper punch 301 was connected to a working electrode and a potential measurement terminal. The lower punch 303 was connected to a counter electrode and a reference electrode. The ionic conductivity of the solid electrolyte material of Example 1 was measured at room temperature by electrochemical impedance measurement. As a result, the ionic conductivity measured at 22°C was 4.4 mS / cm.

[0105] [X-ray diffraction measurement] 4A is a graph showing the X-ray diffraction pattern of the solid electrolyte material according to Example 1. The results shown in the figure were measured by the following method.

[0106] The X-ray diffraction pattern of the solid electrolyte material of Example 1 was measured using an X-ray diffractometer (MiniFlex600, manufactured by RIGAKU) in a dry atmosphere having a dew point of −45° C. or less. Cu-Kα radiation (wavelengths 1.5405 Å and 1.5444 Å) was used as the X-ray source.

[0107] The solid electrolyte material according to Example 1 had a peak at 12.70°.

[0108] [Battery construction] In an argon atmosphere having a dew point of −60° C. or less, the solid electrolyte material according to Example 1 and the positive electrode active material LiCoO2 were prepared in a volume ratio of 50:50. These materials were mixed in a mortar to obtain a positive electrode mixture.

[0109] In an insulating cylinder having an inner diameter of 9.5 mm, the solid electrolyte material (120 mg) according to Example 1 and the above positive electrode mixture (10.6 mg) were stacked to obtain a laminate. A pressure of 360 MPa was applied to this laminate to form a solid electrolyte layer and a first electrode. The solid electrolyte layer had a thickness of 500 μm.

[0110] Next, a Li—In alloy having a thickness of 200 μm was laminated on the solid electrolyte layer, and a pressure of 80 MPa was applied to this laminate to form a second electrode.

[0111] The first electrode was the positive electrode and the second electrode was the negative electrode.

[0112] Current collectors made of stainless steel were attached to the first and second electrodes, and current collecting leads were attached to the current collectors.

[0113] Finally, the inside of the insulating tube was isolated from the outside atmosphere using an insulating ferrule, and the inside of the tube was sealed.

[0114] In this way, the battery according to Example 1 was obtained.

[0115] [Charge / discharge test] Fig. 9 is a graph showing the initial discharge characteristics of the battery according to Example 1. The results shown in Fig. 9 were measured by the following method.

[0116] The battery according to Example 1 was placed in a thermostatic chamber at 25°C.

[0117] The battery according to Example 1 was charged at a current of 56 μA until a voltage of 3.6 V was reached, which corresponds to a 0.05 C rate.

[0118] The cell was then discharged at a current of 56 μA until a voltage of 1.9 V was reached.

[0119] The battery according to Example 1 was charged and discharged at room temperature.

[0120] As a result of the charge-discharge test, the battery according to Example 1 had an initial discharge capacity of 0.86 mAh.

[0121] (Examples 2 to 31 and Comparative Examples 1 and 2) [Preparation of solid electrolyte materials] In Example 2, Li2O2, TaCl5, and ZrCl4 were prepared as raw material powders in a molar ratio of Li2O2:TaCl5:ZrCl4 of 1:1.8:0.2. The mixture was milled and then calcined at 200°C for 3 hours.

[0122] In Example 3, Li2O2, TaCl5, and ZrCl4 were prepared as raw material powders in a Li2O2:TaCl5:ZrCl4 molar ratio of 1:1:1.

[0123] In Example 4, raw material powders of Li2O2, TaCl5, and ZrCl4 were prepared in a molar ratio of Li2O2:TaCl5:ZrCl4 of 1:1:1. The mixture was milled and then calcined at 200 °C for 3 hours.

[0124] In Example 5, Li2O2, TaCl5, ZrCl4, and TaF5 were prepared as raw material powders in a Li2O2:TaCl5:ZrCl4:TaF5 molar ratio of 1:1.702:0.2:0.098.

[0125] In Example 6, raw material powders of Li2O2, TaCl5, ZrCl4, and TaF5 were prepared in a molar ratio of Li2O2:TaCl5:ZrCl4:TaF5 of 1:1.702:0.2:0.098. The mixture was milled and then calcined at 200°C for 3 hours.

[0126] In Example 7, Li2O2, TaCl5, ZrCl4, and TaF5 were prepared as raw material powders in a Li2O2:TaCl5:ZrCl4:TaF5 molar ratio of 1:0.82:0.2:0.98.

[0127] In Example 8, raw material powders of Li2O2, TaCl5, ZrCl4, and TaF5 were prepared in a molar ratio of Li2O2:TaCl5:ZrCl4:TaF5 of 1:0.82:0.2:0.98. The mixture was milled and then calcined at 200°C for 3 hours.

[0128] In Example 9, raw material powders of Li2O2, TaCl5, ZrCl4, and TaBr5 were prepared in a Li2O2:TaCl5:ZrCl4:TaBr5 molar ratio of 1:0.82:0.2:0.98.

[0129] In Example 10, raw material powders of Li2O2, TaCl5, ZrCl4, and TaBr5 were prepared in a molar ratio of Li2O2:TaCl5:ZrCl4:TaBr5 of 1:0.82:0.2:0.98. The mixture was milled and then calcined at 200°C for 3 hours.

[0130] In Example 11, Li2O2, TaBr5, and ZrBr4 were prepared as raw material powders in a Li2O2:TaBr5:ZrBr4 molar ratio of 1:1.8:0.2.

[0131] In Example 12, Li2O2, TaBr5, and ZrBr4 were prepared as raw material powders in a molar ratio of Li2O2:TaBr5:ZrBr4 of 1:1.8:0.2. The mixture was milled and then calcined at 200°C for 3 hours.

[0132] In Example 13, Li2O2, TaCl5, and YCl3 were prepared as raw material powders in a Li2O2:TaCl5:YCl3 molar ratio of 1:1.8:0.2.

[0133] In Example 14, Li2O2, TaCl5, and YCl3 were prepared as raw material powders in a molar ratio of Li2O2:TaCl5:YCl3 of 1:1.8:0.2. The mixture was milled and then calcined at 200 °C for 3 hours.

[0134] In Example 15, Li2O2, TaCl5, and YCl3 were prepared as raw material powders in a Li2O2:TaCl5:YCl3 molar ratio of 1:1.2:0.8.

[0135] In Example 16, Li2O2, TaCl5, and YCl3 were prepared as raw material powders in a molar ratio of Li2O2:TaCl5:YCl3 of 1:1.2:0.8. The mixture was milled and then calcined at 200 °C for 3 hours.

[0136] In Example 17, Li2O2, TaCl5, and LaCl3 were prepared as raw material powders in a Li2O2:TaCl5:LaCl3 molar ratio of 1:1.8:0.2.

[0137] In Example 18, Li2O2, TaCl5, and LaCl3 were prepared as raw material powders in a molar ratio of Li2O2:TaCl5:LaCl3 of 1:1.8:0.2. The mixture was milled and then calcined at 200 °C for 3 hours.

[0138] In Example 19, Li2O2, TaCl5, and LaCl3 were prepared as raw material powders in a Li2O2:TaCl5:LaCl3 molar ratio of 1:1.4:0.6.

[0139] In Example 20, Li2O2, NbCl5, and ZrCl4 were prepared as raw material powders in a Li2O2:NbCl5:ZrCl4 molar ratio of 1:1.8:0.2.

[0140] In Example 21, raw material powders of Li2O2, NbCl5, and ZrCl4 were prepared in a molar ratio of Li2O2:NbCl5:ZrCl4 of 1:1.8:0.2. The mixture was milled and then calcined at 200 °C for 3 hours.

[0141] In Example 22, Li2O2, NbCl5, and ZrCl4 were prepared as raw material powders in a Li2O2:NbCl5:ZrCl4 molar ratio of 1:1.2:0.8.

[0142] In Example 23, raw material powders of Li2O2, NbCl5, and ZrCl4 were prepared in a molar ratio of Li2O2:NbCl5:ZrCl4 of 1:1.2:0.8. The mixture was milled and then calcined at 200 °C for 3 hours.

[0143] In Example 24, raw material powders of Li2O2, NbCl5, ZrCl4, and NbF5 were prepared in a Li2O2:NbCl5:ZrCl4:NbF5 molar ratio of 1:1.31:0.2:0.49.

[0144] In Example 25, raw powders of Li2O2, NbCl5, ZrCl4, and NbF5 were prepared in a molar ratio of Li2O2:NbCl5:ZrCl4:NbF5 of 1:1.31:0.2:0.49. The mixture was milled and then calcined at 200°C for 3 hours.

[0145] In Example 26, raw material powders of Li2O2, NbCl5, ZrCl4, and NbBr5 were prepared in a Li2O2:NbCl5:ZrCl4:Br molar ratio of 1:1.31:0.2:0.49.

[0146] In Example 27, raw powders of Li2O2, NbCl5, ZrCl4, and NbBr5 were prepared in a molar ratio of Li2O2:NbCl5:ZrCl4:NbBr5 of 1:1.31:0.2:0.49. The mixture was milled and then calcined at 200 °C for 3 hours.

[0147] In Example 28, Li2O2, NbCl5, and YCl3 were prepared as raw material powders in a Li2O2:NbCl5:YCl3 molar ratio of 1:1.2:0.8.

[0148] In Example 29, raw material powders of Li2O2, NbCl5, and YCl3 were prepared in a molar ratio of Li2O2:NbCl5:YCl3 of 1:1.2:0.8. The mixture was milled and then calcined at 200 °C for 3 hours.

[0149] In Example 30, Li2O2, NbCl5, and LaCl3 were prepared as raw material powders in a Li2O2:NbCl5:LaCl3 molar ratio of 1:1.8:0.2.

[0150] In Example 31, raw material powders of Li2O2, NbCl5, and LaCl3 were prepared in a Li2O2:NbCl5:LaCl3 molar ratio of 1:1.8:0.2. The mixture was milled and then calcined at 200 °C for 3 hours.

[0151] In Comparative Example 1, Li2O2 and LiCl were prepared as raw material powders so that the molar ratio of Li2O2:LiCl was 1:1.

[0152] In Comparative Example 2, LiCl and TaCl5 were prepared as raw material powders so that the LiCl:TaCl5 molar ratio was 1:1.

[0153] Except for the above, the solid electrolyte materials according to Examples 2 to 31 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1.

[0154] [Evaluation of ionic conductivity] The ionic conductivities of the solid electrolyte materials according to Examples 2 to 31 and Comparative Examples 1 and 2 were measured in the same manner as in Example 1. The measurement results are shown in Tables 1 and 2.

[0155] [X-ray diffraction] The X-ray diffraction patterns of the solid electrolyte materials according to Examples 2 to 31 and Comparative Examples 1 and 2 were measured in the same manner as in Example 1. FIG. 4A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 3, 5, 7, 9, and 11. FIG. 4B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 2, 4, 6, 8, 10, and 12. FIG. 5A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 13 to 16. FIG. 5B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 17 to 19. FIG. 6A is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 20 to 23. FIG. 6B is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 24 to 27. FIG. 7 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Examples 28 to 31. FIG. 8 is a graph showing the X-ray diffraction patterns of the solid electrolyte materials according to Comparative Examples 1 and 2.

[0156] The solid electrolyte material according to Example 2 had a peak at 11.13°.

[0157] The solid electrolyte material according to Example 3 did not have a peak in the first range.

[0158] The solid electrolyte material according to Example 4 did not have a peak in the first range.

[0159] The solid electrolyte material according to Example 5 had a peak at 12.75°.

[0160] The solid electrolyte material according to Example 6 had a peak at 11.83°.

[0161] The solid electrolyte material according to Example 7 had a peak at 13.82°.

[0162] The solid electrolyte material according to Example 8 had a peak at 12.45°.

[0163] The solid electrolyte material according to Example 9 had a peak at 12.50°.

[0164] The solid electrolyte material according to Example 10 had a peak at 11.65°.

[0165] The solid electrolyte material of Example 11 had a peak at 12.52° and also had a peak derived from LiBr.

[0166] The solid electrolyte material of Example 12 had a peak at 12.72° and also had a peak derived from LiBr.

[0167] The solid electrolyte material according to Example 13 had a peak at 12.50°.

[0168] The solid electrolyte material according to Example 14 had a peak at 11.57°.

[0169] The solid electrolyte material according to Example 15 had a peak at 12.41°.

[0170] The solid electrolyte material according to Example 16 did not have a peak in the first range.

[0171] The solid electrolyte material according to Example 17 had a peak at 12.30°.

[0172] The solid electrolyte material according to Example 18 had a peak at 11.66°.

[0173] The solid electrolyte material according to Example 19 did not have a peak in the first range.

[0174] The solid electrolyte material according to Example 20 had a peak at 13.85°.

[0175] The solid electrolyte material according to Example 21 had a peak at 13.89°.

[0176] The solid electrolyte material according to Example 22 had a peak at 13.53°.

[0177] The solid electrolyte material according to Example 23 did not have a peak in the first range.

[0178] The solid electrolyte material according to Example 24 had a peak at 13.25°.

[0179] The solid electrolyte material according to Example 25 had a peak at 13.12°.

[0180] The solid electrolyte material according to Example 26 had a peak at 13.65°.

[0181] The solid electrolyte material according to Example 27 had a peak at 13.60°.

[0182] The solid electrolyte material according to Example 28 had a peak at 14.07°.

[0183] The solid electrolyte material according to Example 29 had a peak at 13.50°.

[0184] The solid electrolyte material according to Example 30 had a peak at 13.75°.

[0185] The solid electrolyte material according to Example 31 had a peak at 13.76°.

[0186] Comparative Examples 1 and 2 did not have a peak in the first range.

[0187] [Table 1]

[0188] [Table 2]

[0189] (Consideration) As is clear from Table 1, the solid electrolyte materials according to Examples 1 to 31 exhibited a thermal conductivity of 1×10 -3 It has high ionic conductivity of more than 1×10 -2 It has high ionic conductivity of more than mS / cm.

[0190] As is clear from a comparison of Examples 22 and 23 with Examples 28 and 29, when M1 is Nb, the ionic conductivity of the solid electrolyte material is higher when M2 is Zr than when it is Y. As is clear from a comparison of Examples 20 and 21 with Examples 30 and 31, when M1 is Nb, the ionic conductivity of the solid electrolyte material is higher when M2 is Zr than when it is La.

[0191] As is clear from a comparison of Example 1 with Examples 13 and 17, when M1 is Ta, the ionic conductivity of the solid electrolyte material is higher when M2 is Zr than when M2 is Y or La.

[0192] As is clear from a comparison of Examples 9, 10, 26, and 27 with Examples 7, 8, 24, and 25, the ionic conductivity of the solid electrolyte material is higher when X is Br and Cl than when X is F and Cl.

[0193] As is clear from a comparison of Examples 1 and 2 with Examples 11 and 12, the ionic conductivity of the solid electrolyte material is higher when X is Cl than when X is Br.

[0194] As is clear from a comparison of Examples 1, 2, 5, and 6 with Examples 7 and 8, when the F / X molar ratio is 0% or more and 5% or less, the ionic conductivity of the solid electrolyte material becomes higher.

[0195] The solid electrolyte materials according to Examples 1 to 31 do not contain sulfur and therefore do not generate hydrogen sulfide.

[0196] As described above, the solid electrolyte material according to the present disclosure has practical lithium ion conductivity and is therefore suitable for providing a battery with excellent charge / discharge characteristics. [Industrial Applicability]

[0197] The battery of the present disclosure is used, for example, in an all-solid-state lithium-ion secondary battery.

Claims

1. A solid electrolyte material consisting essentially of Li, M1, M2, O and X, where: M1 is at least one selected from the group consisting of Ta and Nb; M2 is at least one selected from the group consisting of Zr, Y, and La; X is at least one selected from F, Cl, and Br; a ratio of the total amount of substances of Li, M1, M2, O, and X to the total amount of substances of all elements constituting the solid electrolyte material is 95% or more; In an X-ray diffraction pattern obtained by X-ray diffraction measurement using Cu-Kα radiation, the crystal phase has a peak in the range of diffraction angle 2θ of 11.08° or more and 14.12° or less. Solid electrolyte material.

2. X is at least one selected from the group consisting of Cl and Br; The solid electrolyte material according to claim 1 .

3. The ratio of the amount of substance of M2 to the sum of the amounts of substances of M1 and M2 is greater than 0% and less than or equal to 60%; The solid electrolyte material according to claim 1 or 2.

4. A solid electrolyte material consisting essentially of Li, M1, M2, O and X, where: M1 is at least one selected from the group consisting of Ta and Nb; M2 is at least one selected from the group consisting of Zr, Y, and La; X is at least one selected from the group consisting of Cl and Br; a ratio of the total amount of substances of Li, M1, M2, O, and X to the total amount of substances of all elements constituting the solid electrolyte material is 95% or more; The ratio of the amount of substance of M2 to the sum of the amounts of substances of M1 and M2 is greater than 0% and less than or equal to 60%; Solid electrolyte material.

5. A solid electrolyte material consisting essentially of Li, M1, M2, O and X, where: M1 is at least one selected from the group consisting of Ta and Nb; M2 is at least one selected from the group consisting of Zr, Y, and La; X is at least one selected from F, Cl, and Br; a ratio of the total amount of substances of Li, M1, M2, O, and X to the total amount of substances of all elements constituting the solid electrolyte material is 95% or more; The ratio of the amount of substance of M2 to the sum of the amounts of substances of M1 and M2 is 5% or more and 50% or less; Solid electrolyte material.

6. The ratio of the amount of substance of M2 to the sum of the amounts of substances of M1 and M2 is 10% or more and 50% or less; The solid electrolyte material according to claim 1 .

7. The ratio of the amount of substance of F to the amount of substance of X is 0% or more and 65% or less. The solid electrolyte material according to claim 1 .

8. The ratio of the amount of substance of F to the amount of substance of X is 0% or more and 50% or less. The solid electrolyte material according to claim 7 .

9. The ratio of the amount of substance of F to the amount of substance of X is 0% or more and 5% or less. The solid electrolyte material according to claim 8.

10. M2 is Zr; The solid electrolyte material according to claim 1 .

11. positive electrode, a negative electrode, and an electrolyte layer disposed between the positive electrode and the negative electrode; Equipped with At least one selected from the group consisting of the positive electrode, the negative electrode, and the electrolyte layer contains the solid electrolyte material according to any one of claims 1 to 10. battery.

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