Battery

Abstract

A battery 1000 is provided with a positive electrode 201, a first electrolyte layer 101, a second electrolyte layer 102, a third electrolyte layer 103, and a negative electrode 202 in this order, wherein: the first electrolyte layer 101 contains a first solid electrolyte material; the second electrolyte layer 102 contains a second solid electrolyte material; the third electrolyte layer 103 contains a third solid electrolyte material; the Young's modulus of the second solid electrolyte material is lower than that of both the first solid electrolyte material and the third solid electrolyte material; and the first solid electrolyte material and the third solid electrolyte material are different from each other.

Description

Technical Field

[0001] The present disclosure relates to a battery.

Background Art

[0002] Patent Document 1 discloses an all-solid-state battery in which a positive electrode layer, a first crystalline electrolyte layer, a glass electrolyte layer, a second crystalline electrolyte layer, and a negative electrode layer are laminated in this order.

Prior Art Document

Patent Document

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the prior art, further improvement in the output characteristics of the battery has been desired.

Means for Solving the Problems

[0005] A battery according to one aspect of the present disclosure includes a positive electrode, a first electrolyte layer, a second electrolyte layer, a third electrolyte layer, and a negative electrode in this order. The first electrolyte layer contains a first solid electrolyte material, the second electrolyte layer contains a second solid electrolyte material, the third electrolyte layer contains a third solid electrolyte material, the Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material, and the first solid electrolyte material and the third solid electrolyte material are different materials.

Effects of the Invention

[0006] According to the present disclosure, the output characteristics of the battery can be improved.

Brief Description of the Drawings

[0007]

Figure 1

Figure 2

[0008] (Overview of an Aspect According to the Present Disclosure) The battery according to the first aspect of the present disclosure includes a positive electrode, a first electrolyte layer, a second electrolyte layer, a third electrolyte layer, and a negative electrode, in this order. The first electrolyte layer contains a first solid electrolyte material. The second electrolyte layer contains a second solid electrolyte material. The third electrolyte layer contains a third solid electrolyte material. The Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material. The first solid electrolyte material and the third solid electrolyte material are different materials.

[0009] According to the first aspect, the output characteristics of the battery can be improved.

[0010] In the second aspect of the present disclosure, for example, in the battery according to the first aspect, the thickness of the second electrolyte layer may be smaller than the thickness of the first electrolyte layer and the thickness of the third electrolyte layer. According to such a configuration, the resistance of the second electrolyte layer is reduced, and the output characteristics of the battery can be improved.

[0011] In the third aspect of the present disclosure, for example, in the battery according to the first or second aspect, the first solid electrolyte material may contain Li, M1, and X1, the M1 may be at least one selected from the group consisting of metal elements other than Li and metalloid elements, and the X1 may be at least one selected from the group consisting of F, Cl, Br, and I.

[0012] In a fourth aspect of the present disclosure, for example, in the battery according to the third aspect, the first solid electrolyte material may be represented by the compositional formula (1): Li α1 M1 β1 X1 γ1 where α1, β1, and γ1 may each be a value greater than 0.

[0013] In a fifth aspect of the present disclosure, for example, in the battery according to the third or fourth aspect, the M1 may contain yttrium.

[0014] According to the third to fifth aspects, the ionic conductivity of the first solid electrolyte material can be further improved.

[0015] In a sixth aspect of the present disclosure, for example, in the battery according to any one of the first to fifth aspects, the second solid electrolyte material may be an inorganic solid electrolyte. According to such a configuration, the output characteristics of the battery can be improved.

[0016] In a seventh aspect of the present disclosure, for example, in the battery according to any one of the first to sixth aspects, the second solid electrolyte material may contain Li, M2, and X2. The M2 may be at least one selected from the group consisting of metal elements and metalloid elements other than Li, and the X2 may be at least one selected from the group consisting of F, Cl, Br, and I.

[0017] In an eighth aspect of the present disclosure, for example, in the battery according to the seventh aspect, the second solid electrolyte material may be represented by the compositional formula (2): Li α2 M2 β2 X2 γ2 where α2, β2, and γ2 may each be a value greater than 0.

[0018] In a ninth aspect of the present disclosure, for example, in the battery according to the seventh or eighth aspect, the M2 may contain yttrium.

[0019] According to the 7th to 9th aspects, the ionic conductivity of the second solid electrolyte material can be further improved.

[0020] In the 10th aspect of the present disclosure, for example, in the battery according to any one of the 1st to 9th aspects, the third solid electrolyte material may be a sulfide solid electrolyte. According to such a configuration, the output characteristics of the battery can be improved.

[0021] In the 11th aspect of the present disclosure, for example, in the battery according to any one of the 1st to 9th aspects, the third solid electrolyte material may contain Li, M3, and X3, the M3 may be at least one selected from the group consisting of metal elements and metalloid elements other than Li, and the X3 may be at least one selected from the group consisting of F, Cl, Br, and I.

[0022] In the 12th aspect of the present disclosure, for example, in the battery according to the 11th aspect, the third solid electrolyte material may be represented by the composition formula (3): Li α3 M3 β3 X3 γ3 where α3, β3, and γ3 may each be a value greater than 0.

[0023] In the 13th aspect of the present disclosure, for example, in the battery according to the 11th or 12th aspect, the M3 may contain yttrium.

[0024] According to the 11th to 13th aspects, the ionic conductivity of the third solid electrolyte material can be further improved.

[0025] In a 14th aspect of the present disclosure, for example, in the battery according to any one of the 1st to 13th aspects, the first solid electrolyte material may contain at least one selected from the group consisting of F, Cl, Br, and I, the second solid electrolyte material may contain at least one selected from the group consisting of F, Cl, Br, and I, the third solid electrolyte material may contain at least one selected from the group consisting of F, Cl, Br, and I. In the first solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R1, and in the first solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R2. In the second solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R3, and in the second solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R4. In the third solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R5, and in the third solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R6. When this is the case, the relationship of (R3 + R4) > (R1 + R2) and (R3 + R4) > (R5 + R6) may be satisfied. According to such a configuration, the adhesion between different solid electrolyte layers is improved and peeling is suppressed.

[0026] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings.

[0027] (Embodiment 1) FIG. 1 is a cross-sectional view showing a schematic configuration of a battery 1000 according to Embodiment 1.

[0028] The battery 1000 includes a positive electrode 201, a first electrolyte layer 101, a second electrolyte layer 102, a third electrolyte layer 103, and a negative electrode 202 in this order. The positive electrode 201, the first electrolyte layer 101, the second electrolyte layer 102, the third electrolyte layer 103, and the negative electrode 202 are laminated in this order. The electrolyte layer 100 includes the first electrolyte layer 101, the second electrolyte layer 102, and the third electrolyte layer 103. The electrolyte layer 100 is disposed between the positive electrode 201 and the negative electrode 202. The first electrolyte layer 101 includes a first solid electrolyte material. The second electrolyte layer 102 includes a second solid electrolyte material. The third electrolyte layer 103 includes a third solid electrolyte material. The Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material. The first solid electrolyte material and the third solid electrolyte material are different materials. According to the above configuration, the output characteristics of the battery 1000 can be improved.

[0029] The electrolyte layer 100 has a multilayer structure. Therefore, as the electrolyte layer 100, an electrolyte layer containing a solid electrolyte material having low oxidation resistance and an electrolyte layer containing a solid electrolyte material having low reduction resistance can be used. As the first electrolyte layer 101, for example, a solid electrolyte material having low reduction resistance can be used. As the third electrolyte layer 103, for example, a solid electrolyte material having low oxidation resistance can be used. According to the above configuration, the internal resistance of the electrolyte layer can be reduced, and the output characteristics of the battery 1000 can be improved.

[0030] Patent Document 1 discloses an all-solid-state battery in which a positive electrode layer, a first crystalline electrolyte layer, a glass electrolyte layer, a second crystalline electrolyte layer, and a negative electrode layer are laminated in this order. It is mentioned that the interlayer adhesion is improved by crushing the glass electrolyte layer during press molding. Patent Document 1 does not mention the problems that occur when laminating and joining a plurality of solid electrolyte layers containing different solid electrolyte materials.

[0031] On the one hand, as a result of the inventors' investigation, it was found that when a solid electrolyte layer containing different solid electrolyte materials with different compression characteristics is laminated and compressed to form a laminate of different solid electrolyte layers, peeling occurs due to the residual stress between the different solid electrolyte layers. As a result, the output characteristics of the battery deteriorate. This problem can be solved by arranging an intermediate layer between the different solid electrolyte layers. The intermediate layer contains a solid electrolyte material having a Young's modulus smaller than the Young's modulus of the solid electrolyte materials contained in each of the different solid electrolyte layers. That is, by providing an intermediate layer containing a solid electrolyte material with a small Young's modulus, the adhesion between the different solid electrolyte layers is improved and peeling is suppressed. Thereby, the output characteristics of the battery can be improved.

[0032] The first electrolyte layer 101 may contain a first solid electrolyte material as a main component. The second electrolyte layer 102 may contain a second solid electrolyte material as a main component. The third electrolyte layer 103 may contain a third solid electrolyte material different from the first solid electrolyte material as a main component. The ratio of the mass of the first solid electrolyte material to the mass of the first electrolyte layer 101 may be, for example, 50% by mass or more, or 70% by mass or more. The ratio of the mass of the second solid electrolyte material to the mass of the second electrolyte layer 102 may be, for example, 50% by mass or more, or 70% by mass or more. The ratio of the mass of the third solid electrolyte material to the mass of the third electrolyte layer 103 may be, for example, 50% by mass or more, or 70% by mass or more.

[0033] The first solid electrolyte material contained in the first electrolyte layer 101 may be at least one selected from a first group composed of a plurality of solid electrolyte materials. The first electrolyte layer 101 may have a single-layer structure or a multilayer structure. For example, when the first electrolyte layer 101 is composed of a plurality of layers, each layer may have a different composition.

[0034] The second solid electrolyte material contained in the second electrolyte layer 102 may be at least one selected from a second group consisting of a plurality of solid electrolyte materials. The second electrolyte layer 102 may have a single-layer structure or a multilayer structure. For example, when the second electrolyte layer 102 is composed of a plurality of layers, each layer may have a different composition.

[0035] The third solid electrolyte material contained in the third electrolyte layer 103 may be at least one selected from a third group consisting of a plurality of solid electrolyte materials. The third electrolyte layer 103 may have a single-layer structure or a multilayer structure. For example, when the third electrolyte layer 103 is composed of a plurality of layers, each layer may have a different composition.

[0036] The third solid electrolyte material is a material having a composition different from that of the first solid electrolyte material. In this case, the composition of the first solid electrolyte material contained in the first group is different from the composition of the third solid electrolyte material contained in the third group. However, the first electrolyte layer 101 may partially contain a solid electrolyte material having the same composition as the third electrolyte layer 103. The solid electrolyte material contained in the first electrolyte layer 101 and also contained in the third electrolyte layer 103 may be, for example, 50% or less, 30% or less, or 10% or less in terms of volume ratio with respect to the first electrolyte layer 101. The third electrolyte layer 103 may partially contain a solid electrolyte material having the same composition as the first electrolyte layer 101. The solid electrolyte material contained in the third electrolyte layer 103 and also contained in the first electrolyte layer 101 may be, for example, 50% or less, 30% or less, or 10% or less in terms of volume ratio with respect to the third electrolyte layer 103.

[0037] The Young's modulus of the second solid electrolyte material contained in the second electrolyte layer 102 may be smaller than the Young's modulus of the first solid electrolyte material contained in the first electrolyte layer 101 and the Young's modulus of the third solid electrolyte material contained in the third electrolyte layer 103.

[0038] By disposing an intermediate layer containing a solid electrolyte material with a low Young's modulus between different solid electrolyte layers, that is, by providing an intermediate layer containing a solid electrolyte material with a low Young's modulus, the residual stress between the different solid electrolyte layers is relaxed. As a result, the adhesion between the different solid electrolyte layers is improved and peeling is suppressed. Consequently, a battery 1000 having excellent output characteristics can be obtained.

[0039] The method for measuring the Young's modulus of the solid electrolyte material is not limited. For example, the nanoindentation method may be used. Specifically, the Young's modulus of a microregion can be obtained by pushing the indenter of a nanoindenter into the solid electrolyte material and measuring the displacement amount when a load is applied to the solid electrolyte material. Also, for example, an ultrasonic pulser-receiver may be used.

[0040] <Solid electrolyte material> In the present disclosure, the "semi-metal element" refers to B, Si, Ge, As, Sb, and Te. The "metal element" refers to all elements included in Groups 1 to 12 of the periodic table excluding hydrogen, and all elements included in Groups 13 to 16 of the periodic table excluding B, Si, Ge, As, Sb, Te, C, N, P, O, S, and Se. That is, the "semi-metal element" or "metal element" is a group of elements that can become cations when forming an inorganic compound with a halogen element.

[0041] The first solid electrolyte material can be a material containing Li, M1, and X1. Here, the element M1 is at least one selected from the group consisting of metal elements and semi-metal elements other than Li. The element X1 is at least one selected from the group consisting of F, Cl, Br, and I. According to the above configuration, the ionic conductivity of the first solid electrolyte material can be further improved. As a result, the output characteristics of the battery 1000 can be further improved. Also, the thermal stability of the battery 1000 can be improved. When the first solid electrolyte material does not contain sulfur, the generation of hydrogen sulfide gas can be suppressed.

[0042] The first solid electrolyte material may be, for example, a material represented by the following compositional formula (1).

[0043] Li α1 M1 β1 X1 γ1 ··· Formula (1)

[0044] Here, α1, β1, and γ1 are each values greater than 0. γ1 can be, for example, 4, 6, etc. According to the above configuration, the ionic conductivity of the first solid electrolyte material can be improved. Thereby, the output characteristics of the battery 1000 can be improved.

[0045] The second solid electrolyte material may contain an inorganic solid electrolyte. The second solid electrolyte material may be an inorganic solid electrolyte. According to the above configuration, the resistance of the second electrolyte layer can be reduced, and the output characteristics of the battery 1000 can be improved.

[0046] The second solid electrolyte material can be a material containing Li, M2, and X2. Here, the element M2 is at least one selected from the group consisting of metal elements and metalloid elements other than Li. The element X2 is at least one selected from the group consisting of F, Cl, Br, and I. According to the above configuration, the ionic conductivity of the second solid electrolyte material can be further improved. Thereby, the output characteristics of the battery 1000 can be further improved. Also, the thermal stability of the battery 1000 can be improved. When the second solid electrolyte material does not contain sulfur, the generation of hydrogen sulfide gas can be suppressed.

[0047] The second solid electrolyte material may be, for example, a material represented by the following compositional formula (2).

[0048] Li α2 M2 β2 X2 γ2 ··· Formula (2)

[0049] Here, α2, β2, and γ2 are each values greater than 0. γ2 can be, for example, 4, 6, etc. According to the above configuration, the ionic conductivity of the second solid electrolyte material can be improved. Thereby, the output characteristics of the battery 1000 can be improved.

[0050] The third solid electrolyte material can be a sulfide solid electrolyte material. In the present disclosure, "sulfide solid electrolyte" refers to a solid electrolyte containing sulfur. Examples of sulfide solid electrolytes include Li2S-P2S5, Li2S-SiS2, Li2S-B2S3, Li2S-GeS2, Li 3.25 Ge 0.25 P 0.75 S4, Li 10 GeP2S 12 and the like. Further, LiX, Li2O, MO q , Li p MO q etc. may be added thereto. Here, the element X is at least one selected from the group consisting of F, Cl, Br, and I. Further, the element M is at least one selected from the group consisting of P, Si, Ge, B, Al, Ga, In, Fe, and Zn. p and q are each natural numbers. According to the above configuration, the output characteristics of the battery 1000 can be further improved. One or more sulfide solid electrolytes selected from the above materials can be used.

[0051] The third solid electrolyte material can also be a material containing Li, M3, and X3. Here, the element M3 is at least one selected from the group consisting of metal elements and metalloid elements other than Li. The element X3 is at least one selected from the group consisting of F, Cl, Br, and I. According to the above configuration, the ionic conductivity of the third solid electrolyte material can be further improved. Thereby, the output characteristics of the battery 1000 can be further improved. Also, the thermal stability of the battery 1000 can be improved. When the third solid electrolyte material does not contain sulfur, the generation of hydrogen sulfide gas can be suppressed.

[0052] For example, the third solid electrolyte material may be a material represented by the following compositional formula (3), for example.

[0053] Li α3 M3 β3 X3 γ3 ··· Formula (3)

[0054] Here, α3, β3, and γ3 are each values greater than 0. γ3 can be, for example, 4, 6, etc. According to the above configuration, the ionic conductivity of the third solid electrolyte material can be improved. Thereby, the output characteristics of the battery 1000 can be improved.

[0055] In compositional formula (1), the element M1 may contain Y (= yttrium). In compositional formula (2), the element M2 may contain Y (= yttrium). In compositional formula (3), the element M3 may contain Y (= yttrium). That is, each of the first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may contain Y as a metal element. According to the above configuration, the ionic conductivity of the solid electrolyte material can be further improved. Thereby, the charge and discharge characteristics of the battery 1000 can be further improved.

[0056] The first solid electrolyte material containing Y, the second solid electrolyte material containing Y, and the third solid electrolyte material containing Y may each be, for example, a compound represented by the compositional formula of Li a Me b Y c X6. Here, a + mb + 3c = 6, and c > 0 are satisfied. The element Me is at least one selected from the group consisting of metal elements and metalloid elements excluding Li and Y. m is the valence of the element Me. The element X is at least one selected from the group consisting of F, Cl, Br, and I.

[0057] The element Me may be, for example, 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.

[0058] As the first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material, for example, the following materials can be used respectively. According to the following configuration, the ionic conductivity of the first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material can be further improved. Thereby, the output characteristics of the battery 1000 can be further improved.

[0059] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following composition formula (A1).

[0060] Li 6-3d Y d X6 ··· Formula (A1)

[0061] In the composition formula (A1), the element X is at least one selected from the group consisting of Cl, Br, and I. Also, 0 < d < 2 is satisfied.

[0062] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following composition formula (A2).

[0063] Li3YX6 ··· Formula (A2)

[0064] In the composition formula (A2), the element X is at least one selected from the group consisting of Cl, Br, and I.

[0065] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following composition formula (A3).

[0066] Li 3-3δ Y 1+δ Cl6 ··· Formula (A3)

[0067] In the composition formula (A3), 0 < δ ≦ 0.15 is satisfied.

[0068] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following compositional formula (A4).

[0069] Li 3-3δ Y 1+δ Br6···Formula (A4)

[0070] In the compositional formula (A4), 0 < δ ≦ 0.25 is satisfied.

[0071] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following compositional formula (A5).

[0072] Li 3-3δ+a Y 1+δ-a Me a Cl 6-x-y Br x I y ···Formula (A5)

[0073] In the compositional formula (A5), the element Me is at least one selected from the group consisting of Mg, Ca, Sr, Ba, and Zn. -1 < δ < 2, 0 < a < 3, 0 < (3 - 3δ + a), 0 < (1 + δ - a), 0 ≦ x ≦ 6, 0 ≦ y ≦ 6, and (x + y) ≦ 6 are satisfied.

[0074] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following compositional formula (A6).

[0075] Li 3-3δ Y 1+δ-a Me a Cl 6-x-y Br x I y ···Formula (A6)

[0076] In the compositional formula (A6), the element Me is at least one selected from the group consisting of Al, Sc, Ga, and Bi. -1 < δ < 1, 0 < a < 2, 0 < (1 + δ - a), 0 ≦ x ≦ 6, 0 ≦ y ≦ 6, and (x + y) ≦ 6 are satisfied.

[0077] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following compositional formula (A7).

[0078] Li 3-3δ-a Y 1+δ-a Me a Cl 6-x-y Br x I y ··· Formula (A7)

[0079] In the compositional formula (A7), the element Me is at least one selected from the group consisting of Zr, Hf, and Ti. -1 < δ < 1, 0 < a < 1.5, 0 < (3 - 3δ - a), 0 < (1 + δ - a), 0 ≤ x ≤ 6, 0 ≤ y ≤ 6, and (x + y) ≤ 6 are satisfied.

[0080] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may be materials represented by the following compositional formula (A8).

[0081] Li 3-3δ-2a Y 1+δ-a Me a Cl 6-x-y Br x I y ··· Formula (A8)

[0082] In the compositional formula (A8), the element Me is at least one selected from the group consisting of Ta and Nb. -1 < δ < 1, 0 < a < 1.2, 0 < (3 - 3δ - 2a), 0 < (1 + δ - a), 0 ≤ x ≤ 6, 0 ≤ y ≤ 6, and (x + y) ≤ 6 are satisfied.

[0083] As the first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material, more specifically, for example, Li3YX6, Li2MgX4, Li2FeX4, Li(Al, Ga, In)X4, Li3(Al, Ga, In)X6, etc. can be used. Here, the element X is at least one selected from the group consisting of Cl, Br, and I. In the present disclosure, "(Al, Ga, In)" indicates at least one element selected from the group of elements within the parentheses. That is, "(Al, Ga, In)" is synonymous with "at least one selected from the group consisting of Al, Ga, and In". The same applies to other elements.

[0084] The first solid electrolyte material contains, for example, at least one selected from the group consisting of F, Cl, Br, and I. The second solid electrolyte material contains, for example, at least one selected from the group consisting of F, Cl, Br, and I. The third solid electrolyte material contains, for example, at least one selected from the group consisting of F, Cl, Br, and I. In the first solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R1. In the first solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R2. In the second solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R3. In the second solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R4. In the third solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R5. In the third solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R6. In this case, the relationship of (R3 + R4) > (R1 + R2) and (R3 + R4) > (R5 + R6) may be satisfied. R1, R2, R3, R4, R5, and R6 may each be zero.

[0085] When the solid electrolyte material contains a large amount of Br and / or I, the binding force between anions and cations is weak. Br and I are anions with large ionic radii. The cations are Li and M. As a result, the solid electrolyte material can have a soft crystal structure. That is, when the solid electrolyte material contains a large amount of Br and / or I, the solid electrolyte material can have a small Young's modulus. In the solid electrolyte material, the larger the sum of the ratio of the amount of substance of Br to the total amount of substance of halogen and the ratio of the amount of substance of I, the smaller the Young's modulus of the solid electrolyte material. For the above reasons, when the relationships of (R3 + R4) > (R1 + R2) and (R3 + R4) > (R5 + R6) are satisfied, the Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material. As a result, the adhesion between different solid electrolyte layers can be improved and peeling can be suppressed. Thereby, the output characteristics of the battery 1000 can be improved.

[0086] When the first solid electrolyte material is a material represented by, for example, Li3YCl 6-x1-y1 Br x1 I y1 R1 and R2 are respectively represented by R1 = x1 / 6 and R2 = y1 / 6. When the second solid electrolyte material is a material represented by, for example, Li3YCl 6-x2-y2 Br x2 I y2 R3 and R4 are respectively represented by R3 = x2 / 6 and R4 = y2 / 6. When the third solid electrolyte material is a material represented by, for example, Li3YCl 6-x3-y3 Br x3 I y3 R5 and R6 are respectively represented by R5 = x3 / 6 and R6 = y3 / 6.

[0087] By appropriately selecting the elements of M1 contained in the first solid electrolyte material, M2 contained in the second solid electrolyte material, and M3 contained in the third solid electrolyte material, the Young's modulus of the solid electrolyte material can also be changed.

[0088] By appropriately selecting the combination of M1 and X1 included in the first solid electrolyte material, the Young's modulus of the first solid electrolyte material can be changed. When M1 has the same valence as the ions of X1 and M1 has a large ionic radius, the binding force between M1 and X1 is weak. Alternatively, when M1 has an ionic radius approximately the same as that of X1 and M1 has a small valence, the binding force between M1 and X1 is weak. As a result, the first solid electrolyte material can adopt a soft crystal structure.

[0089] By appropriately selecting the combination of M2 and X2 included in the second solid electrolyte material, the Young's modulus of the second solid electrolyte material can be changed. When M2 has the same valence as the ions of X2 and M2 has a large ionic radius, the binding force between M2 and X2 is weak. Alternatively, when M2 has an ionic radius approximately the same as that of X2 and M2 has a small valence, the binding force between M2 and X2 is weak. As a result, the second solid electrolyte material can adopt a soft crystal structure.

[0090] By appropriately selecting the combination of M3 and X3 included in the third solid electrolyte material, the Young's modulus of the third solid electrolyte material can be changed. When M3 has the same valence as the ions of X3 and M3 has a large ionic radius, the binding force between M3 and X3 is weak. Alternatively, when M3 has an ionic radius approximately the same as that of X3 and M3 has a small valence, the binding force between M3 and X3 is weak. As a result, the third solid electrolyte material can adopt a soft crystal structure.

[0091] The first electrolyte layer 101 may contain, for example, the above-described first solid electrolyte material as a main component. That is, the mass ratio of the first solid electrolyte material to the whole of the first electrolyte layer 101 may be, for example, 50% by mass or more, or may be 70% by mass or more. According to the above configuration, the charge / discharge characteristics of the battery 1000 can be further improved.

[0092] The first electrolyte layer 101 may contain 100% by mass of the first solid electrolyte material, for example, excluding inevitably mixed impurities, with respect to the whole of the first electrolyte layer 101. That is, the first electrolyte layer 101 may be substantially composed of only the first solid electrolyte material. According to the above configuration, the charge and discharge characteristics of the battery 1000 can be further improved.

[0093] The first electrolyte layer 101 contains the first solid electrolyte material as a main component, and may further contain inevitable impurities, or starting materials, by-products, and decomposition products used when synthesizing the first solid electrolyte material.

[0094] The second electrolyte layer 102 may contain, for example, the above second solid electrolyte material as a main component. That is, the mass ratio of the second solid electrolyte material with respect to the whole of the second electrolyte layer 102 may be, for example, 50% by mass or more, or 70% by mass or more. According to the above configuration, the charge and discharge characteristics of the battery 1000 can be further improved.

[0095] The second electrolyte layer 102 may contain 100% by mass of the second solid electrolyte material, for example, excluding inevitably mixed impurities, with respect to the whole of the second electrolyte layer 102. That is, the second electrolyte layer 102 may be substantially composed of only the second solid electrolyte material. According to the above configuration, the charge and discharge characteristics of the battery 1000 can be further improved.

[0096] The second electrolyte layer 102 contains the second solid electrolyte material as a main component, and may further contain inevitable impurities, or starting materials, by-products, and decomposition products used when synthesizing the second solid electrolyte material.

[0097] The third electrolyte layer 103 may contain, for example, the above third solid electrolyte material as a main component. That is, the mass ratio of the third solid electrolyte material with respect to the whole of the third electrolyte layer 103 may be, for example, 50% by mass or more, or 70% by mass or more. According to the above configuration, the charge and discharge characteristics of the battery 1000 can be further improved.

[0098] The third electrolyte layer 103 may contain the third solid electrolyte material at a mass ratio of 100% with respect to the entire third electrolyte layer 103, for example, excluding inevitably mixed impurities. That is, the third electrolyte layer 103 may be substantially composed of only the third solid electrolyte material. According to the above configuration, the charge and discharge characteristics of the battery 1000 can be further improved.

[0099] The third electrolyte layer 103 may contain the third solid electrolyte material as a main component, and may further contain inevitable impurities, or starting materials, by-products, and decomposition products used when synthesizing the third solid electrolyte material.

[0100] The first solid electrolyte material, the second solid electrolyte material, and the third solid electrolyte material may each be a compound containing Li, M4, X4, and O (oxygen). Here, the element M4 includes at least one selected from the group consisting of, for example, Nb and Ta. Also, the element X4 is at least one selected from the group consisting of Cl, Br, and I.

[0101] The compound containing Li, M4, X4, and O (oxygen) may be a material represented by, for example, the following composition formula (4).

[0102] Li x M4O y X4 5+x-2y ··· Formula (4)

[0103] Here, x may satisfy 0.1 < x < 7.0. y may satisfy 0.4 < y < 1.9. According to the above configuration, the solid electrolyte material has high ionic conductivity. If this solid electrolyte material is used, the battery 1000 can exhibit excellent charge and discharge efficiency.

[0104] At least one of the positive electrode 201 and the negative electrode 202 may contain an electrolyte material, for example, may contain a solid electrolyte material. As the solid electrolyte material contained in the electrode, for example, a sulfide solid electrolyte, an oxide solid electrolyte, a halide solid electrolyte, a polymer solid electrolyte, a complex hydride solid electrolyte, etc. may be used. The solid electrolyte material may be, for example, a first solid electrolyte material, a second solid electrolyte material, and a third solid electrolyte material.

[0105] In the present disclosure, the "oxide solid electrolyte" refers to a solid electrolyte containing oxygen. Here, the oxide solid electrolyte may further contain an anion other than sulfur and halogen elements as an anion other than oxygen. In the present disclosure, the "halide solid electrolyte" refers to a solid electrolyte containing a halogen element and not containing sulfur.

[0106] As the sulfide solid electrolyte, the above sulfide solid electrolyte exemplified as the third solid electrolyte material may be used.

[0107] As the oxide solid electrolyte, for example, NASICON-type solid electrolytes typified by LiTi2(PO4)3 and its element substitution products, perovskite-type solid electrolytes of the (LaLi)TiO3 system, Li 14 ZnGe4O 16 , Li4SiO4, LiGeO4 and its element substitution products typified by LISICON-type solid electrolytes, Li7La3Zr2O 12 and its element substitution products typified by garnet-type solid electrolytes, Li3PO4 and its N substitution products, and glasses or glass ceramics to which Li2SO4, Li2CO3, etc. are added based on Li-B-O compounds such as LiBO2, Li3BO3, etc. may be used.

[0108] As the halide solid electrolyte, the compound represented by the above composition formula (1) exemplified as the first solid electrolyte material may be used. As the halide solid electrolyte, the compound represented by the above composition formula (2) exemplified as the second solid electrolyte material may be used. As the halide solid electrolyte, the compound represented by the above composition formula (3) exemplified as the third solid electrolyte material may be used. As the halide solid electrolyte, the compound containing the above-mentioned Li, M4, X4 and O (oxygen) may be used. As the halide solid electrolyte, the compound represented by the above composition formula (4) may be used.

[0109] As the polymer solid electrolyte, for example, a compound of a polymer compound and a lithium salt can be used. The polymer compound may have an ethylene oxide structure. The polymer compound having an ethylene oxide structure can contain a large amount of lithium salt. Therefore, the ionic conductivity can be further increased. As the lithium salt, LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), and LiC(SO2CF3)3 etc. can be used. One or more lithium salts selected from the above lithium salts can be used.

[0110] As the complex hydride solid electrolyte, for example, LiBH4-LiI, LiBH4-P2S5 etc. can be used.

[0111] The shape of the solid electrolyte material contained in the battery 1000 is not limited. The shape of the solid electrolyte material may be, for example, needle-like, spherical, and ellipsoidal etc. The shape of the solid electrolyte material may be, for example, particulate.

[0112] The positive electrode 201 includes, for example, as a positive electrode active material, a material having the property of occluding and releasing metal ions (e.g., lithium ions). As the positive electrode active material, for example, lithium-containing transition metal oxides, transition metal fluorides, polyanion materials, fluorinated polyanion materials, transition metal sulfides, transition metal oxysulfides, and transition metal oxynitrides can be used. Examples of lithium-containing transition metal oxides include Li(Ni, Co, Al)O2, Li(Ni, Co, Mn)O2, LiCoO2, etc. In particular, when a lithium-containing transition metal oxide is used as the positive electrode active material, the manufacturing cost can be reduced and the average discharge voltage can be increased. Further, in order to increase the energy density of the battery, the positive electrode active material may be lithium nickel cobalt manganese oxide. For example, the positive electrode active material may be Li(Ni, Co, Mn)O2.

[0113] When the shape of the solid electrolyte material contained in the positive electrode 201 is particulate (e.g., spherical), the median diameter of the solid electrolyte material may be 100 μm or less. When the median diameter of the solid electrolyte material is 100 μm or less, the positive electrode active material and the solid electrolyte material can form a good dispersion state in the positive electrode 201. Thereby, the charge and discharge characteristics of the battery 1000 are improved.

[0114] The median diameter of the solid electrolyte material contained in the positive electrode 201 may be smaller than the median diameter of the positive electrode active material. Thereby, the solid electrolyte material and the positive electrode active material can form a good dispersion state.

[0115] The median diameter of the positive electrode active material may be 0.1 μm or more and 100 μm or less. When the median diameter of the positive electrode active material is 0.1 μm or more, the positive electrode active material and the solid electrolyte material can form a good dispersion state in the positive electrode 201. Therefore, the charge and discharge characteristics of the battery 1000 are improved. When the median diameter of the positive electrode active material is 100 μm or less, the lithium diffusion rate in the positive electrode active material becomes fast. Therefore, the battery 1000 can operate at high power.

[0116] In this specification, the median diameter of particles means the particle diameter (d50) corresponding to 50% volume cumulative, which is obtained from the particle size distribution measured on a volume basis by the laser diffraction scattering method. The particle size distribution can also be measured, for example, using an image analyzer. The same applies to other materials.

[0117] Regarding the volume ratio "v1:100 - v1" of the positive electrode active material and the solid electrolyte material contained in the positive electrode 201, 30 ≤ v1 ≤ 95 may be satisfied. Here, v1 represents the volume ratio of the positive electrode active material when the total volume of the positive electrode active material and the solid electrolyte material contained in the positive electrode 201 is 100. When 30 ≤ v1 is satisfied, sufficient battery energy density can be ensured. When v1 ≤ 95 is satisfied, the battery 1000 can operate at high power.

[0118] The thickness of the positive electrode 201 may be 10 μm or more and 500 μm or less. When the thickness of the positive electrode 201 is 10 μm or more, sufficient battery energy density can be ensured. When the thickness of the positive electrode 201 is 500 μm or less, the battery 1000 can operate at high power.

[0119] The thickness of each of the first electrolyte layer 101, the second electrolyte layer 102, and the third electrolyte layer 103 may be 0.1 μm or more and 300 μm or less. When the thickness of each of the first electrolyte layer 101, the second electrolyte layer 102, and the third electrolyte layer 103 is 0.1 μm or more, it becomes difficult for the positive electrode 201 and the negative electrode 202 to short-circuit. When the thickness of each of the first electrolyte layer 101, the second electrolyte layer 102, and the third electrolyte layer 103 is 300 μm or less, the battery 1000 can operate at high power.

[0120] The thickness of the second electrolyte layer 102 may be smaller than the thickness of the first electrolyte layer 101 and the thickness of the third electrolyte layer 103. According to the above configuration, the second electrolyte layer 102 can suppress the peeling between different solid electrolyte layers. In addition, the resistance of the second electrolyte layer 102 is reduced, and the output characteristics of the battery 1000 can be improved.

[0121] The negative electrode 202 includes, for example, as a negative electrode active material, a material having the property of occluding and releasing metal ions (for example, lithium ions). As the negative electrode active material, a metal material, a carbon material, an oxide, a nitride, a tin compound, a silicon compound, etc. can be used. The metal material may be a single metal. The metal material may be an alloy. Examples of the metal material include lithium metal and lithium alloy. Examples of the carbon material include natural graphite, coke, carbon in the process of graphitization, carbon fiber, spherical carbon, artificial graphite, and amorphous carbon. The use of silicon (Si), tin (Sn), silicon compounds, tin compounds, etc. can improve the capacity density.

[0122] The median diameter of the negative electrode active material may be 0.1 μm or more and 100 μm or less. When the median diameter of the negative electrode active material is 0.1 μm or more, in the negative electrode 202, the negative electrode active material and the solid electrolyte material can form a good dispersion state. Thereby, the charge and discharge characteristics of the battery 1000 are improved. When the median diameter of the negative electrode active material is 100 μm or less, the lithium diffusion rate in the negative electrode active material becomes fast. Therefore, the battery 1000 can operate at high power.

[0123] The median diameter of the negative electrode active material may be larger than the median diameter of the solid electrolyte material. Thereby, the negative electrode active material and the solid electrolyte material can form a good dispersion state.

[0124] Regarding the volume ratio "v2:100 - v2" of the negative electrode active material and the solid electrolyte material contained in the negative electrode 202, 30 ≤ v2 ≤ 95 may be satisfied. Here, v2 represents the volume ratio of the negative electrode active material when the total volume of the negative electrode active material and the solid electrolyte material contained in the negative electrode 202 is 100. When 30 ≤ v2 is satisfied, a sufficient energy density of the battery can be ensured. When v2 ≤ 95 is satisfied, the battery 1000 can operate at high power.

[0125] The thickness of the negative electrode 202 may be 10 μm or more and 500 μm or less. When the thickness of the negative electrode 202 is 10 μm or more, sufficient battery energy density can be ensured. When the thickness of the negative electrode 202 is 500 μm or less, the battery 1000 can operate at high power.

[0126] The positive electrode active material and the negative electrode active material may be coated with a coating material in order to reduce the interfacial resistance between each active material and the solid electrolyte material. As the coating material, a material with low electron conductivity can be used. As the coating material, an oxide material, an oxide solid electrolyte, etc. can be used.

[0127] As the oxide material, for example, SiO2, Al2O3, TiO2, B2O3, Nb2O5, WO3, and ZrO2, etc. can be used.

[0128] As the oxide solid electrolyte that can be used as the coating material, Li-Nb-O compounds such as LiNbO3, Li-B-O compounds such as LiBO2 and Li3BO3, Li-Al-O compounds such as LiAlO2, Li-Si-O compounds such as Li4SiO4, Li2SO4, Li4Ti5O 12 and other Li-Ti-O compounds, Li-Zr-O compounds such as Li2ZrO3, Li-Mo-O compounds such as Li2MoO3, Li-V-O compounds such as LiV2O5, Li-W-O compounds such as Li2WO4 can be mentioned. The oxide solid electrolyte has high ionic conductivity. The oxide solid electrolyte has excellent high potential stability. Therefore, by using the oxide solid electrolyte as the coating material, the charge and discharge efficiency of the battery 1000 can be further improved.

[0129] At least one selected from the group consisting of the positive electrode 201, the first electrolyte layer 101, the second electrolyte layer 102, the third electrolyte layer 103, and the negative electrode 202 may contain a non-aqueous electrolyte solution, a gel electrolyte, or an ionic liquid for the purpose of facilitating the transfer of lithium ions and improving the output characteristics of the battery 1000.

[0130] The non-aqueous electrolyte contains a non-aqueous solvent and a lithium salt dissolved in the non-aqueous solvent. As the non-aqueous solvent, a cyclic carbonate solvent, a linear carbonate solvent, a cyclic ether solvent, a linear ether solvent, a cyclic ester solvent, a linear ester solvent, a fluorine solvent, etc. can be used. Examples of the cyclic carbonate solvent include ethylene carbonate, propylene carbonate, butylene carbonate, etc. Examples of the linear carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, etc. Examples of the cyclic ether solvent include tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, etc. Examples of the linear ether solvent include 1,2-dimethoxyethane, 1,2-diethoxyethane, etc. Examples of the cyclic ester solvent include γ-butyrolactone, etc. Examples of the linear ester solvent include methyl acetate, etc. Examples of the fluorine solvent include fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, fluorodimethylenecarbonate, etc. As the non-aqueous solvent, one non-aqueous solvent selected from these may be used alone, or a mixture of two or more non-aqueous solvents selected from these may be used.

[0131] The non-aqueous electrolyte may contain at least one fluorine solvent selected from the group consisting of fluoroethylene carbonate, methyl fluoropropionate, fluorobenzene, fluoroethyl methyl carbonate, and fluorodimethylenecarbonate.

[0132] As the lithium salt, LiPF6, LiBF4, LiSbF6, LiAsF6, LiSO3CF3, LiN(SO2F)2, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2CF3)(SO2C4F9), LiC(SO2CF3)3, etc. can be used. As the lithium salt, one lithium salt selected from these may be used alone, or 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 / liter or more and 2 mol / liter or less.

[0133] As a gel electrolyte, a polymer material impregnated with a non-aqueous electrolyte can be used. As the polymer material, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, a polymer having an ethylene oxide bond, etc. can be used.

[0134] The cation constituting the ionic liquid may be an aliphatic chain quaternary salt such as tetraalkylammonium or tetraalkylphosphonium, an aliphatic cyclic ammonium such as pyrrolidinium, morpholinium, imidazolinium, tetrahydropyrimidinium, piperazinium, piperidinium, etc., a nitrogen-containing heteroaromatic cation such as pyridinium or imidazolium, etc. The anion constituting the ionic liquid is PF6 - 、BF4 - 、SbF6 - 、AsF6 - 、SO3CF3 - 、N(SO2F)2 - 、N(SO2CF3)2 - 、N(SO2C2F5)2 - 、N(SO2CF3)(SO2C4F9) - 、C(SO2CF3)3 - etc. may be used. The ionic liquid may contain a lithium salt.

[0135] At least one selected from the group consisting of the positive electrode 201, the first electrolyte layer 101, the second electrolyte layer 102, the third electrolyte layer 103, and the negative electrode 202 may contain a binder for the purpose of improving the adhesion between particles. The binder is used to improve the binding property of the materials constituting the electrode. Examples of the binder include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, methyl polyacrylate ester, ethyl polyacrylate ester, hexyl polyacrylate ester, polymethacrylic acid, methyl polymethacrylate ester, ethyl polymethacrylate ester, hexyl polymethacrylate ester, polyvinyl acetate, polyvinylpyrrolidone, polyether, polyethersulfone, hexafluoropolypropylene, styrene butadiene rubber, carboxymethyl cellulose, and the like. 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 can also be used as the binder. A mixture of two or more selected from the above materials may be used as the binder.

[0136] At least one of the positive electrode 201 and the negative electrode 202 may contain a conductive aid for the purpose of enhancing electron conductivity. Examples of the conductive aid include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black and ketjen black, conductive fibers such as carbon fiber and metal fiber, metal powders such as carbon fluoride and aluminum, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and conductive polymer compounds such as polyaniline, polypyrrole, and polythiophene. When a carbon conductive aid is used as the conductive aid, cost reduction can be achieved.

[0137] The shape of the battery 1000 includes, for example, coin type, cylindrical type, rectangular type, sheet type, button type, flat type, and laminated type.

[0138] The battery 1000 composed of the positive electrode 201, the first electrolyte layer 101, the second electrolyte layer 102, the third electrolyte layer 103, and the negative electrode 202 may be laminated in plurality via a current collector. By electrically connecting a plurality of batteries in series, the voltage of the battery can be increased. By electrically connecting a plurality of batteries in parallel, the capacity of the battery can be increased. By electrically connecting a plurality of batteries in series and in parallel, the voltage and capacity of the battery can be increased.

[0139] <Method for manufacturing a solid electrolyte material> The solid electrolyte material represented by the composition formula (1) can be manufactured, for example, by the following method.

[0140] First, according to the target composition, a plurality of raw material powders of binary halides are prepared. The binary halide refers to a compound composed of two elements containing a halogen element. For example, when preparing Li3YCl6, the raw material powder LiCl and the raw material powder YCl3 are prepared at a molar ratio of 3:1. At this time, by selecting the type of raw material powder, the elements of "M1" and "X1" in the composition formula (1) are determined. Also, by adjusting the type of raw material powder, the blending ratio of the raw material powder, and the synthesis process, the values of "α1", "β1", and "γ1" in the composition formula (1) are determined.

[0141] After mixing and pulverizing the raw material powders, the raw material powders are reacted with each other using the method of mechanochemical milling. Alternatively, after mixing and pulverizing the raw material powders, they may be sintered in a vacuum or an inert atmosphere. For example, firing may be performed within the range of 100 °C or higher and 400 °C or lower for 1 hour or more. By these methods, a solid electrolyte material is obtained.

[0142] Note that the crystal phase constitution (that is, the crystal structure) of the solid electrolyte material can be determined by adjusting the reaction method and reaction conditions of the raw material powders with each other.

[0143] <Method for manufacturing a battery> The battery 1000 using the solid electrolyte material manufactured above can be manufactured, for example, by the following method.

[0144] Figure 2 is a diagram for explaining the manufacturing method of the battery 1000. As shown in Figure 2, the lower die 1 is inserted into the insulating tube 3. The powder of the third solid electrolyte material is put into the insulating tube 3. The upper die 2 is inserted into the insulating tube 3, and the powder of the third solid electrolyte material is pressed to form the third electrolyte layer 103. The upper die 2 is removed, and the powder of the second solid electrolyte material is put into the insulating tube 3. The upper die 2 is inserted into the insulating tube 3 again, and the powder of the second solid electrolyte material is pressed to form the second electrolyte layer 102 on the third electrolyte layer 103. The upper die 2 is removed, and the powder of the first solid electrolyte material is put into the insulating tube 3. The upper die 2 is inserted into the insulating tube 3 again, and the powder of the first solid electrolyte material is pressed to form the first electrolyte layer 101 on the second electrolyte layer 102. The upper die 2 is removed, and the powder of the positive electrode active material is put into the insulating tube 3. The upper die 2 is inserted into the insulating tube 3 again, and the powder of the first solid electrolyte material is pressed to form the positive electrode 201 on the first electrolyte layer 101.

[0145] After forming the positive electrode 201, the lower die 1 is removed, and the powder of the negative electrode active material, the disk-shaped punched metal indium foil or the disk-shaped punched metal lithium foil is put into the insulating tube 3. The lower die 1 is inserted again, and the powder of the negative electrode active material, the metal indium foil or the metal lithium foil is pressed to form the negative electrode 202. Thereby, the power generation element 10 is formed.

[0146] After forming the power generation element 10, the lower die 1 and the upper die 2 are fixed with the insulating tube 4, the bolt 5 and the nut 6. Thereby, the battery 1000 is obtained.

Industrial Applicability

[0147] The battery of the present disclosure can be used, for example, as an all-solid-state lithium-ion secondary battery or the like.

Explanation of Reference Numerals

[0148] 1 Lower die 2 Upper die 3 Insulating tube 4 Insulating tube 5 Bolt 6 Nut 10 Power generation element 1000 Battery 100 Electrolyte layer 101 First electrolyte layer 102 Second electrolyte layer 103 Third electrolyte layer 201 Positive electrode 202 Negative electrode

Claims

1. A battery comprising a positive electrode, a first electrolyte layer, a second electrolyte layer, a third electrolyte layer, and a negative electrode in this order, wherein the first electrolyte layer contains a first solid electrolyte material, the second electrolyte layer contains a second solid electrolyte material, the third electrolyte layer contains a third solid electrolyte material, the first solid electrolyte material contains Li, M1, and X1, M1 is at least one selected from the group consisting of metal elements other than Li and metalloid elements, X1 is at least one selected from the group consisting of F, Cl, Br, and I, the second solid electrolyte material contains Li, M2, and X2, M2 is at least one selected from the group consisting of metal elements other than Li and metalloid elements, X2 is at least one selected from the group consisting of F, Cl, Br, and I, the third solid electrolyte material contains Li, M3, and X3, M3 is at least one selected from the group consisting of metal elements other than Li and metalloid elements, X3 is at least one selected from the group consisting of F, Cl, Br, and I, the Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material, the first solid electrolyte material and the third solid electrolyte material are different materials, a battery.

2. The thickness of the second electrolyte layer is smaller than the thickness of the first electrolyte layer and the thickness of the third electrolyte layer, a battery according to Claim 1.

3. The first solid electrolyte material is represented by the following compositional formula (1), Li α1 M1 β1 X1 γ1 ... Equation (1) where α1, β1, and γ1 are each values greater than 0, a battery according to Claim 1 or 2.

4. The second solid electrolyte material is represented by the following compositional formula (2), Li α2 M2 β2 X2 γ2 ... Equation (2) where α2, β2, and γ2 are each values greater than 0, a battery according to any one of Claims 1 to 3.

5. The third solid electrolyte material is represented by the following compositional formula (3), Li α3 M3 β3 X3 γ3 ... Equation (3) where α3, β3, and γ3 are each values greater than 0, a battery according to any one of Claims 1 to 4.

6. M1 contains yttrium, M2 contains yttrium, M3 contains yttrium, a battery according to any one of Claims 1 to 5.

7. A battery comprising a positive electrode, a first electrolyte layer, a second electrolyte layer, a third electrolyte layer, and a negative electrode in this order, The first electrolyte layer contains a first solid electrolyte material, The second electrolyte layer contains a second solid electrolyte material, The third electrolyte layer contains a third solid electrolyte material, The first solid electrolyte material contains Li, M1, and X1, The M1 is at least one selected from the group consisting of metal elements and metalloid elements other than Li, and contains yttrium, The X1 is at least one selected from the group consisting of F, Cl, Br, and I, The second solid electrolyte material contains Li, M2, and X2, The M2 is at least one selected from the group consisting of metal elements and metalloid elements other than Li, and contains yttrium, The X2 is at least one selected from the group consisting of F, Cl, Br, and I, The third solid electrolyte material contains Li, M3, and X3, The M3 is at least one selected from the group consisting of metal elements and metalloid elements other than Li, and contains yttrium, The X3 is at least one selected from the group consisting of F, Cl, Br, and I, The first solid electrolyte material and the third solid electrolyte material are different materials, In the first solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R1, In the first solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R2, In the second solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R3, In the second solid electrolyte material, the ratio of the amount of substance of I to the total amount of substance of halogen is defined as R4, In the third solid electrolyte material, the ratio of the amount of substance of Br to the total amount of substance of halogen is defined as R5, When the ratio of the amount of substance of I to the total amount of substance of halogen in the third solid electrolyte material is defined as R6, It satisfies the relationships of (R3 + R4) > (R1 + R2) and (R3 + R4) > (R5 + R6), Battery.

8. The thickness of the second electrolyte layer is smaller than the thickness of the first electrolyte layer and the thickness of the third electrolyte layer, The battery according to claim 7.

9. The first solid electrolyte material is represented by the following compositional formula (1), Li α1 M1 β1 X1 γ1 ··· Formula (1) α1, β1, and γ1 are each values greater than 0, The second solid electrolyte material is represented by the following compositional formula (2), Liα2M2β2X2γ2... Formula (2) α2, β2, and γ2 are each values greater than 0, The third solid electrolyte material is represented by the following compositional formula (3), Liα3M3β3X3γ3... Formula (3) α3, β3, and γ3 are each values greater than 0, The battery according to claim 7 or 8.

10. A battery comprising a positive electrode, a first electrolyte layer, a second electrolyte layer, a third electrolyte layer, and a negative electrode, in this order, The first electrolyte layer contains a first solid electrolyte material, The second electrolyte layer contains a second solid electrolyte material, The third electrolyte layer contains a third solid electrolyte material, The first solid electrolyte material contains Li, M1, and X1, The M1 is at least one selected from the group consisting of metal elements and metalloid elements other than Li, The X1 is at least one selected from the group consisting of F, Cl, Br, and I, The second solid electrolyte material contains Li, M2, and X2, The M2 is at least one selected from the group consisting of metal elements and metalloid elements other than Li, The X2 is at least one selected from the group consisting of F, Cl, Br, and I, The third solid electrolyte material is a sulfide solid electrolyte, The Young's modulus of the second solid electrolyte material is smaller than the Young's modulus of the first solid electrolyte material and the Young's modulus of the third solid electrolyte material, Battery.

11. The thickness of the second electrolyte layer is smaller than the thickness of the first electrolyte layer and the thickness of the third electrolyte layer, The battery according to claim 10.

12. The first solid electrolyte material is represented by the following compositional formula (1), Liα1M1β1X1γ1... Formula (1) α1, β1, and γ1 are each values greater than 0, The second solid electrolyte material is represented by the following compositional formula (2), Liα2M2β2X2γ2... Formula (2) α2, β2, and γ2 are each values greater than 0, The battery according to claim 10 or 11.

13. The M1 contains yttrium, The M2 contains yttrium, The battery according to any one of claims 10 to 12.

14. The sulfide solid electrolyte contains at least one selected from the group consisting of Li 2 S-P 2 S 5, Li 2 S-SiS 2, Li 2 S-B 2 S 3, Li 2 S-GeS 2, Li 3.25 Ge 0.25 P 0.75 S 4, and Li 10 GeP 2 S 12. The battery according to any one of claims 10 to 13.

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