Battery

Abstract

A battery 1000 according to the present disclosure conforms with at least one configuration that is selected from the group consisting of (I) and (II) described below.　(I) At least one layer that is selected from the group consisting of a first electrode layer 100, a second electrode layer 200, and a solid electrolyte layer 300 contains a solid electrolyte that contains a halogenated oxide.　(II) The battery 1000 additionally comprises a side surface layer which contains a solid electrolyte that contains a halogenated oxide, and which is disposed on a side surface of at least one layer that is selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the solid electrolyte layer 300.　The halogenated oxide includes at least one substance that is selected from the group consisting of a halogenated oxide A which is composed of Li, M1, X1, and O, and a halogenated oxide B which is composed of Li, M2, X2, and O. M1 represents at least one element that is selected from the group consisting of trivalent metal elements and trivalent metalloid elements, and M2 represents at least one element that is selected from the group consisting of tetravalent metal elements and tetravalent metalloid elements. X1 and X2 each represent at least one element that is selected from the group consisting of F, Cl, Br, and I.

Description

battery

[0001] The present disclosure relates to batteries.

[0002] Patent Document 1 discloses a battery using a solid electrolyte containing Li, Ti, M, and X that coats an active material. M is at least one selected from the group consisting of metal elements and semimetal elements other than Li and Ti, and X is at least one selected from halogen elements. In Patent Document 1, the solid electrolyte is contained in a coating layer that coats the active material.

[0003] International Publication No. 2023 / 037769

[0004] There is a need in the art for a highly reliable battery. Therefore, the present disclosure provides a battery with improved reliability by increasing mechanical strength.

[0005] The battery of the present disclosure comprises: a first electrode layer; a second electrode layer; and a solid electrolyte layer disposed between the first electrode layer and the second electrode layer, wherein the battery satisfies at least one of the following conditions (I) and (II): (I) at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer comprises a solid electrolyte containing a halogenated oxide. (II) The battery further comprises a side layer, the side layer comprising a solid electrolyte containing a halogenated oxide, disposed on a side surface of at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer. The halogenated oxide includes at least one selected from the group consisting of halogenated oxide A consisting of Li, M1, X1, and O, and halogenated oxide B consisting of Li, M2, X2, and O; in the halogenated oxide A, M1 is at least one element selected from the group consisting of trivalent metal elements and trivalent metalloid elements, and X1 is at least one element selected from the group consisting of F, Cl, Br, and I; and in the halogenated oxide B, M2 is at least one element selected from the group consisting of tetravalent metal elements and tetravalent metalloid elements, and X2 is at least one element selected from the group consisting of F, Cl, Br, and I.

[0006] The present disclosure can provide batteries with improved reliability.

[0007] FIG. 1 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1000 according to a first embodiment. FIG. 2 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1100 according to a second embodiment. FIG. 3 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1200 according to a third embodiment. FIG. 4 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1300 according to a fourth embodiment. FIG. 5 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1400 according to a fifth embodiment. FIG. 6 is a cross-sectional view and a plan view showing the schematic configuration of a battery 1500 according to a sixth embodiment.

[0008] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings.

[0009] The embodiments described below are all comprehensive or specific examples. The numerical values, shapes, materials, component placement and connection configurations, manufacturing processes, and the order of manufacturing processes shown in the following embodiments are merely examples and are not intended to limit the present disclosure. Furthermore, among the components in the following embodiments, components that are not described in the independent claims that represent the highest concepts are described as optional components.

[0010] In this specification, terms indicating the relationship between elements, such as parallelism, terms indicating the shape of elements, such as rectangle, and numerical ranges are not expressions that only express a strict meaning, but are expressions that also include a substantially equivalent range, for example, a difference of about a few percent.

[0011] The drawings are schematic diagrams and are not necessarily drawn to scale. Therefore, for example, the scales of the drawings do not necessarily match. In the drawings, the same reference numerals are used for substantially the same components, and redundant explanations are omitted or simplified.

[0012] In this specification and the drawings, the x-axis, y-axis, and z-axis represent the three axes of a three-dimensional Cartesian coordinate system. In each embodiment, the z-axis direction is the thickness direction of the battery. Furthermore, in this specification, unless otherwise specified, the "thickness direction" refers to the direction perpendicular to the plane on which each layer of the battery is stacked.

[0013] In this specification, the term "plan view" refers to the view of the battery along the stacking direction of the layers in the battery. The term "thickness" refers to the length of the battery and each layer in the stacking direction.

[0014] In this specification, unless otherwise specified, in a battery and each layer, a "side surface" means a surface along the stacking direction of each layer in the battery, and a "main surface" means a surface other than the side surface.

[0015] In this specification, the terms "inside" and "outside" refer to the center side of the battery as "inside" and the peripheral side of the battery as "outside" when the battery is viewed along the stacking direction of the layers in the battery.

[0016] In this specification, the terms "upper" and "lower" in the battery configuration do not refer to the upper direction (vertically upper) and lower direction (vertically lower) in absolute spatial recognition, but are used as terms defined by a relative positional relationship based on the stacking order in the stacking configuration. Furthermore, the terms "upper" and "lower" are used not only when two components are arranged with a gap between them and another component is present between them, but also when two components are arranged closely together and the two components are in contact with each other.

[0017] First Embodiment A battery according to a first embodiment will be described below.

[0018] The battery according to the first embodiment includes a first electrode layer, a second electrode layer, and a solid electrolyte layer, the electrolyte layer being disposed between the first and second electrode layers.

[0019] The battery according to the first embodiment satisfies at least one of the following conditions (I) and (II): (I) at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer includes a solid electrolyte containing a halogenated oxide. (II) The battery further includes a side layer including a solid electrolyte containing a halogenated oxide, disposed on a side surface of at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer.

[0020] The halogenated oxide includes at least one selected from the group consisting of halogenated oxide A consisting of Li, M1, X1, and O, and halogenated oxide B consisting of Li, M2, X2, and O. In halogenated oxide A, M1 is at least one element selected from the group consisting of trivalent metal elements and trivalent metalloid elements, and X1 is at least one element selected from the group consisting of F, Cl, Br, and I. In halogenated oxide B, M2 is at least one element selected from the group consisting of tetravalent metal elements and tetravalent metalloid elements, and X2 is at least one element selected from the group consisting of F, Cl, Br, and I.

[0021] Halogenated oxides are generally harder than halides, and in particular, the above-described halogenated oxide A and halogenated oxide B are harder than, for example, conventional halide solid electrolytes contained in batteries. By including a solid electrolyte containing at least one selected from the group consisting of halogenated oxide A and halogenated oxide B, the battery according to the first embodiment can improve its reliability.

[0022] When a solid electrolyte containing halogenated oxide A is included in the battery according to the first embodiment, the solid electrolyte containing halogenated oxide A acts as a reinforcing material or an anchor material between particles (e.g., between solid electrolyte particles, between active material particles, or between solid electrolyte particles and active material particles). Therefore, in the battery according to the first embodiment, the inclusion of halogenated oxide A improves external impact resistance and strength. The desired impact resistance and strength can be adjusted by selecting the type of halogen element constituting halogenated oxide A and the oxygen content in halogenated oxide A, thereby achieving high battery reliability. Thus, the inclusion of a solid electrolyte containing halogenated oxide A improves the reliability of the battery according to the first embodiment. Hereinafter, in the embodiments of the present disclosure, a solid electrolyte containing halogenated oxide A as an essential component may be referred to as "solid electrolyte A" to distinguish it from other solid electrolytes.

[0023] The above-described effects of solid electrolyte A can be achieved whether the battery according to the first embodiment satisfies either of the above configurations (I) and (II). For example, when the above configuration (I) is satisfied, the strength of the electrode layer and / or electrolyte layer, which are the power-generating elements of the battery, can be improved, thereby improving the reliability of the battery. Furthermore, when the above configuration (II) is satisfied, the side layer containing solid electrolyte A can effectively suppress structural defects (i.e., cracks or peeling originating from the side) that tend to originate from the side surface of the battery and are susceptible to the effects of external and thermal shocks, thereby improving the reliability of the battery.

[0024] When a solid electrolyte containing a halogenated oxide B is included in the battery according to the first embodiment, the solid electrolyte containing the halogenated oxide B suppresses densification of components containing the solid electrolyte (e.g., solid electrolyte layer, electrode layer, etc.), increasing the number of pores and lowering the density. This reduces the heat capacity of components such as the solid electrolyte layer and electrode layer, thereby reducing cracks caused by thermal shock and thermal cycles. This results in a battery with excellent durability against external stress and resistance to thermal shock. The type of halogen element constituting the halogenated oxide B and the oxygen content in the halogenated oxide B can be adjusted to the desired impact resistance and thermal shock resistance, thereby achieving high battery reliability. Thus, the inclusion of a solid electrolyte containing a halogenated oxide B improves the reliability of the battery according to the first embodiment. Hereinafter, in the embodiments of the present disclosure, a solid electrolyte containing a halogenated oxide B may be referred to as "solid electrolyte B" to distinguish it from other solid electrolytes.

[0025] The above-described effects of solid electrolyte B can be achieved whether the battery according to the first embodiment satisfies either of the above configurations (I) and (II). For example, when the above configuration (I) is satisfied, the impact resistance and thermal shock resistance of the electrode layer and / or electrolyte layer, which are the power generating elements of the battery, can be improved, thereby improving the reliability of the battery. Furthermore, when the above configuration (II) is satisfied, the side layer containing solid electrolyte B can effectively suppress structural defects (i.e., cracks or peeling originating from the side) that tend to originate from the side surface of the battery, where the effects of external and thermal shocks are likely to become apparent, thereby improving the reliability of the battery.

[0026] A configuration example of the battery according to the first embodiment will be described below. The configuration example described below is an example in which the battery according to the first embodiment satisfies the above configuration (I).

[0027] FIG. 1 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1000 according to a first embodiment.

[0028] Fig. 1(a) shows a cross-sectional view of a battery 1000 according to the first embodiment. Fig. 1(b) is a plan view of the battery 1000 according to the first embodiment as seen from below in the z-axis direction. Fig. 1(a) shows a cross section taken along line II in Fig. 1(b).

[0029] As shown in FIG. 1 , the battery 1000 includes a first electrode layer 100, a second electrode layer 200 arranged parallel to and facing the first electrode layer 100, and a solid electrolyte layer 300 located between the first electrode layer 100 and the second electrode layer 200. In other words, the battery 1000 includes the first electrode layer 100, the solid electrolyte layer 300, and the second electrode layer 200, in this order in the stacking direction. For example, the first electrode layer 100 and the solid electrolyte layer 300 include at least one selected from the group consisting of solid electrolyte A and solid electrolyte B. The included solid electrolyte A may be particulate solid electrolyte A (hereinafter referred to as "particles of solid electrolyte A") 400. The included solid electrolyte B may be particulate solid electrolyte B (hereinafter referred to as "particles of solid electrolyte B") 400. That is, the particles indicated by the reference numeral 400 in the figure are particles of solid electrolyte A or solid electrolyte B. Hereinafter, the particles 400 of solid electrolyte A or the particles 400 of solid electrolyte B may be collectively referred to as solid electrolyte particles 400. The battery 1000 is, for example, an all-solid-state battery.

[0030] The first electrode layer 100 includes a first current collector 110 and a first active material layer 120. For example, the first active material layer 120 includes particles 400 of solid electrolyte A. The second electrode layer 200 includes a second current collector 210 and a second active material layer 220. The solid electrolyte layer 300 includes particles 400 of solid electrolyte A, is located between the first active material layer 120 and the second active material layer 220, and is in contact with each of the first active material layer 120 and the second active material layer 220. In the battery 1000 shown in FIG. 1 , the solid electrolyte particles 400 are included only in the first electrode layer 100 and the solid electrolyte layer 300, but the second electrode layer 200 may also include solid electrolyte particles 400.

[0031] 1 , the first current collector 110, the first active material layer 120, the solid electrolyte layer 300, the second active material layer 220, and the second current collector 210 each have a roughly rectangular shape in a plan view. However, in the battery according to the first embodiment, the shapes of these components are not limited to a rectangle.

[0032] 1 , the first current collector 110, the first active material layer 120, the solid electrolyte layer 300, the second active material layer 220, and the second current collector 210 are all the same size and have the same outline in a plan view, but this is not limiting. For example, the first active material layer 120 may be smaller than the second active material layer 220. The first active material layer 120 and the second active material layer 220 may be smaller than the solid electrolyte layer 300. For example, a portion of the solid electrolyte layer 300 may be in contact with at least one of the first current collector 110 and the second current collector 210.

[0033] In the battery 1000 according to the first embodiment, for example, the first electrode layer 100 is a positive electrode layer, and the second electrode layer 200 is a negative electrode layer. In this case, specifically, the first current collector 110 is a positive electrode current collector, and the first active material layer 120 is a positive electrode active material layer. Furthermore, the second current collector 210 is a negative electrode current collector, and the second active material layer 220 is a negative electrode active material layer.

[0034] The first electrode layer 100 may be a negative electrode, and the second electrode layer 200 may be a positive electrode. Specifically, the first current collector 110 may be a negative electrode current collector, and the first active material layer 120 may be a negative electrode active material layer. The second current collector 210 may be a positive electrode current collector, and the second active material layer 220 may be a positive electrode active material layer.

[0035] In the following description, the positive electrode active material layer and the negative electrode active material layer may be collectively referred to simply as "active material layers." Furthermore, the positive electrode current collector and the negative electrode current collector may be collectively referred to simply as "current collectors."

[0036] Hereinafter, a solid electrolyte A containing a halogenated oxide A as an essential component and a solid electrolyte B containing a halogenated oxide B as an essential component will be described.

[0037] (Solid Electrolyte A) As described above, the solid electrolyte A contains a halogenated oxide, and the halogenated oxide contains a halogenated oxide A composed of Li, M1, X1, and O.

[0038] The halogenated oxide in solid electrolyte A may further contain halogenated oxide B composed of Li, M2, X2, and O. When the halogenated oxide in solid electrolyte A contains halogenated oxide A and halogenated oxide B, the ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O in halogenated oxide A (O / (X1+O)) may be equal to or greater than the ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O in halogenated oxide B (O / (X2+O)), i.e., the relationship O / (X1+O)≧O / (X2+O) may be satisfied. For example, the characteristics of halogenated oxide A and halogenated oxide B can be controlled over a wide range by varying the content ratio of halogenated oxide A and halogenated oxide B, the type of halogen element constituting these halogenated oxides, and the oxygen content ratio. This enables control over a wider range to improve battery characteristics and reliability. The ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)) can be regarded as the oxygen content in halogenated oxide A. The ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)) can be regarded as the oxygen content in halogenated oxide B.

[0039] For example, halogenated oxide A tends to have a higher melting point and be harder than halogenated oxide B. By making the oxygen content of halogenated oxide A equal to or greater than the oxygen content of halogenated oxide B, the solid electrolyte A's function as a reinforcing material and an anchor material between particles becomes more effective. Furthermore, by including halogenated oxide B, which is softer than halogenated oxide A, the solid electrolyte A not only ensures interparticle adhesion but also absorbs expansion and contraction during charge / discharge and thermal cycles. This results in the densification of the components of the battery 1000 and the suppression of structural defects. This allows for the realization of a battery 1000 with excellent mechanical strength and higher reliability.

[0040] The solid electrolyte A may further contain a halide. Halides share a structure with halide oxides in that they both contain a halogen element. Therefore, halides have a thermal expansion coefficient similar to that of halide oxides, good bondability, and good affinity with halide oxides. By including a halide in addition to a halide oxide in the solid electrolyte A, the battery 1000 according to the first embodiment is able to suppress the occurrence of structural defects (e.g., interfacial peeling between the solid electrolyte and the halide oxide, and the occurrence of cracks) due to charge / discharge cycles and thermal shock, thereby achieving high reliability.

[0041] The solid electrolyte A may further contain a halide A consisting of Li, M1, and X1. That is, the solid electrolyte A may contain a halide A containing elements common to the halide oxide A (i.e., Li, M1, and X1). The halide A has a thermal expansion coefficient close to that of the halide oxide A, good bonding properties, and good affinity with the halide oxide A. This allows for the production of a solid electrolyte A having high, excellent ionic conductivity, for example, of 1 μS / cm or more. Therefore, a battery 1000 with high reliability and excellent performance can be obtained.

[0042] The solid electrolyte A may further contain a halide B consisting of Li, M2, and X2. That is, the solid electrolyte A may contain a halide B containing elements common to the halide oxide B (i.e., Li, M2, and X2). The halide B has a thermal expansion coefficient close to that of the halide oxide B, good bonding properties, and good affinity with the halide oxide B. As a result, when the solid electrolyte A contains the halide oxide B and the halide B, a solid electrolyte A having high and excellent ionic conductivity, for example, 1 μS / cm or more, can be obtained. Therefore, a battery 1000 with high reliability and excellent performance can be obtained.

[0043] The solid electrolyte A included in the battery 1000 according to the first embodiment may be particulate, such as the solid electrolyte A particles 400. When the solid electrolyte A is particulate, it can be included in the first electrode layer, the second electrode layer, and the solid electrolyte layer together with other solid electrolytes. For example, the solid electrolyte A can also be included in the coating layer of the active material particles. That is, when the solid electrolyte A is included in the electrode layer and the solid electrolyte layer 300, the options for the form of the solid electrolyte A are expanded. Therefore, the desired components can be provided with improved impact resistance and strength at the microstructure level (e.g., particle level). This allows for a highly reliable battery 1000. Furthermore, this configuration allows the battery of the present disclosure to be applied to all-solid-state batteries formed from a compact, such as those formed using sulfide-based solid electrolytes and halide-based solid electrolytes, which have excellent ionic conductivity. This allows for a highly reliable all-solid-state battery with excellent performance. Furthermore, for example, by using finely pulverized particles 400 of solid electrolyte A (for example, particles having a particle diameter of 1 μm or less), it is possible to make the solid electrolyte layer 300 thinner and the coating layer of the active material particles or the like thinner, thereby improving the capacity of the battery 1000.

[0044] The particles 400 of the solid electrolyte A are, for example, uniformly dispersed within the first electrode layer 100 and the solid electrolyte layer 300 .

[0045] The size of the particles 400 of solid electrolyte A can be appropriately selected depending on the first electrode layer 100 and solid electrolyte layer 300 containing the particles 400 (e.g., depending on the sizes of the active material particles and solid electrolyte particles), and may, for example, have an average particle diameter of 0.05 μm or more and 10 μm or less. In FIG. 1 , the particles 400 of solid electrolyte A are shown to have a spherical particle shape, but they may also have a particle shape other than a spherical shape, such as a scale shape.

[0046] It is desirable that the particle diameter of the particles 400 of solid electrolyte A is small. This allows the particles 400 of solid electrolyte A to be uniformly dispersed throughout the first electrode layer 100 and the solid electrolyte layer 300, thereby increasing the surface area of ​​the particles 400 of solid electrolyte A (for example, a BET specific surface area of ​​10 m 2 / g or more). As a result, the contact area between the particles 400 of solid electrolyte A and the surrounding active material or solid electrolyte can be increased. Therefore, the mechanical reliability (flexural strength) of the first electrode layer 100 and the solid electrolyte layer 300 is further improved by miniaturizing the particles 400 of solid electrolyte A (for example, miniaturizing the particles to a diameter of 1 μm or less).

[0047] The particles 400 of solid electrolyte A may contain a halogenated oxide and a halide. When the particles 400 of solid electrolyte A contain both a halide and a hard halogenated oxide, the adhesion between particles is improved. Therefore, for desired components, the effects of improving impact resistance and strength can be obtained at the microstructure level (e.g., particle level). In particular, the effects of improving inter-particle bonding and strength can be obtained in a powder compact. This configuration provides a battery 1000 with excellent reliability, particularly in terms of impact resistance and flexural strength.

[0048] The particles 400 of solid electrolyte A may contain an oxide halide. That is, the oxide halide may be present in the internal region of the particles 400 of solid electrolyte A. This results in the hard oxide halide being disposed inside the particles and a softer material, such as a halide, being disposed on the particle surface, thereby enhancing the interparticle bonding strength and providing the hard core portion within the particles with a reinforcing effect. This results in high interparticle bonding strength and improved strength, particularly in a powder compact.

[0049] The volume fraction of the halogenated oxide in the particles 400 of solid electrolyte A increases, for example, as the volume of the particles 400 of solid electrolyte A increases. This allows the particles 400 of solid electrolyte A to be given softness (e.g., deformability) or hardness, which can be adjusted over a wide range by, for example, changing the particle size. Furthermore, since the gaps between the large, hard particles with a larger volume fraction of halogenated oxide are filled with the small, soft particles with a smaller volume fraction of halogenated oxide, the bonding strength between the particles 400 of solid electrolyte A is further improved. Therefore, the bonding strength and strength between the particles 400 of solid electrolyte A are improved, particularly in a compact.

[0050] The solid electrolyte A particle 400 may have multiple regions where a halide oxide is present. This allows the softness (e.g., deformability) or hardness of the solid electrolyte A particle 400 to be adjusted over a wider range. This improves the reliability of the battery 1000 against external stresses and thermal cycles. The softness or hardness of the solid electrolyte A particle 400 can be adjusted by adjusting the size and number of the regions where a halide oxide is present. Such particles having multiple regions where a halide oxide is present within the particle can be formed, for example, by mixing a halide oxide powder obtained by halogenating an oxide with a halide solid electrolyte by a mechanochemical method to form composite particles. Furthermore, particles having multiple regions where a halide oxide is present within the particle can also be formed by oxidizing a halide having a scale-like or needle-like shape.

[0051] In the halogenated oxide A, M1 may contain Al. This allows the solid electrolyte A to have high ionic conductivity, for example, of 1 μS / cm or more, and high heat resistance due to a melting point, for example, of 750° C. or more. This makes it possible to obtain a battery 1000 with even better performance and heat resistance. In addition, in this case, by increasing the oxygen content in the halogenated oxide A, the heat resistance and hardness of the solid electrolyte A are further improved, thereby further improving the reliability of the battery 1000.

[0052] In the halogenated oxide A, X1 may contain F. By including F in the halogenated oxide A, the solid electrolyte A containing the halogenated oxide A can have high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 600°C or more. Therefore, a battery with higher reliability can be obtained. Here, excellent atmospheric stability means, for example, excellent durability against normal atmospheric moisture.

[0053] In the halide oxide B, M2 may contain Ti. This allows the solid electrolyte A to have high ionic conductivity, for example, of 1 μS / cm or more. Furthermore, when M2 in the halide oxide B contains Ti, the melting point of the halide oxide B is lowered, making the halide oxide B softer. This allows the solid electrolyte A to have high impact resistance. Therefore, a battery with even better performance and impact resistance can be obtained. The softness derived from the halide oxide B decreases with an increase in the oxygen content in the halide oxide B. Therefore, to further improve the impact resistance, the oxygen content in the halide oxide B is limited. For example, by making the oxygen content smaller than that of the halide oxide A, the halide oxide B can be made softer than the halide oxide A.

[0054] In the halogenated oxide B, X2 may contain F. When the halogenated oxide B contains F, the solid electrolyte A containing the halogenated oxide B has high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 600°C or more. Therefore, a battery with higher reliability can be obtained. Here, excellent atmospheric stability means, for example, excellent durability against normal atmospheric moisture.

[0055] The halide oxide contained in the solid electrolyte A may contain at least one element selected from the group consisting of Na, K, Ca, Si, Zr, Ga, P, and Nb. These elements act as auxiliary agents to promote the solid-phase reaction during the synthesis of the halide oxide, thereby lowering the solid-phase reaction temperature of the halide oxide and homogenizing the reaction state. This reduces deviation from the desired composition due to evaporation of constituent components and compositional variation in the halide oxide. Therefore, a solid electrolyte A with excellent properties can be obtained. Furthermore, the inclusion of these elements prevents the halide oxide from sintering too hard, making it easier to pulverize the halide oxide and enabling fine pulverization (e.g., into particles with a particle size of 1 μm or less). This increases the surface area of ​​the halide oxide, further enhancing the effects of the solid electrolyte A (e.g., its function as a reinforcing material and an anchor material between particles). Furthermore, finely divided halide oxides can be used in batteries that require thinner layers.

[0056] The solid electrolyte A may contain a crystalline phase represented by the following composition formula (1): Li3AlX36 Formula (1)

[0057] In the composition formula (1), X3 is at least one selected from the group consisting of F, Cl, Br, and I.

[0058] This provides the solid electrolyte layer A with high ionic conductivity, for example, 1 μS / cm or more, and high reliability, thereby providing a battery with even greater reliability.

[0059] The solid electrolyte A may contain a crystalline phase represented by the following composition formula (2): LiAlF Formula (2)

[0060] This allows the solid electrolyte layer A to be further stable in the atmosphere. Therefore, fluctuations in the properties of the solid electrolyte layer A during the manufacturing process can be suppressed, allowing desired properties to be reproducibly obtained. Furthermore, strict dew point environmental control (i.e., temperature and humidity control) during the manufacturing process is no longer necessary, thereby reducing the manufacturing cost of the battery.

[0061] The halogenated oxide A may contain an amorphous portion A. This can impart softness to the halogenated oxide A, thereby improving the densification of the solid electrolyte A and the adhesion between particles. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (e.g., thermal stress), resulting in a battery 1000 with excellent performance and reliability.

[0062] The amorphous portion A may have a composition represented by the following composition formula (5): Li3M1(X1 1-a O a / 2 )6...Formula (5)

[0063] In the composition formula (5), a satisfies 0<a<1.

[0064] Therefore, the halogenated oxide A can be regarded as a composite material containing a soft material and a hard material. Therefore, the mechanical strength can be further improved by the effect of the halogenated oxide A while improving densification and interparticle binding. Therefore, a battery 1000 with higher reliability can be obtained.

[0065] In the amorphous portion A, M1 may contain Al. This allows the solid electrolyte A to have atmospheric stability, high-temperature durability up to about 800°C, and high ionic conductivity of, for example, 1 μS / cm or more. As a result, a more reliable battery 1000 can be obtained.

[0066] The halogenated oxide A may further contain at least one element selected from the group consisting of Na, Ca, Si, Zr, and Ga. These elements act as auxiliary agents that promote the solid-state reaction when synthesizing the halogenated oxide A, thereby lowering the solid-state reaction temperature of the halogenated oxide A and homogenizing the reaction state. This reduces deviation from the desired composition of the halogenated oxide A due to evaporation of the constituent components, and reduces compositional variation. As a result, a solid electrolyte A having excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength, can be obtained.

[0067] The halogenated oxide B may have a lower melting point than the halogenated oxide A. When the halogenated oxide B has a lower melting point than the halogenated oxide A, the halogenated oxide B is typically softer than the halogenated oxide A. Therefore, for example, when the solid electrolyte A is contained in an electrode layer, the halogenated oxide B tends to deform and fill voids in the solid electrolyte layer and / or electrode layer formed by a mixture containing the halogenated oxide A or another solid electrolyte. Filling of the halogenated oxide B into such voids occurs, for example, when stacking and pressurizing the layers during battery production. Therefore, the solid electrolyte layer and / or electrode layer containing the solid electrolyte A tends to become densified. Note that, in commonly used hot pressing, the halogenated oxide B in particular becomes more deformable. This densification improves, for example, the ionic conductivity of the solid electrolyte layer and / or electrode layer and suppresses the occurrence of structural defects (e.g., voids and cracks). This reduces the occurrence of minute voids and cracks, which are the starting points for deterioration of characteristics due to external stress and thermal cycles, thereby providing a highly reliable solid electrolyte layer and / or electrode layer, thereby realizing a battery 1000 with good performance and excellent reliability.

[0068] The halogenated oxide B may be softer than the halogenated oxide A. For example, when the solid electrolyte A is contained in the electrode layer, the halogenated oxide B, which is softer than the halogenated oxide A, is likely to deform and fill voids in the solid electrolyte layer and / or electrode layer formed by a mixture containing the halogenated oxide A or another solid electrolyte. The filling of such voids with the halogenated oxide B occurs, for example, when stacking and pressurizing the layers during battery production. Therefore, the solid electrolyte layer and / or electrode layer containing the solid electrolyte A is likely to be densified. This densification improves the ionic conductivity of the solid electrolyte layer and / or electrode layer and suppresses the occurrence of structural defects (e.g., voids and cracks). Furthermore, the soft halogenated oxide B reduces springback after pressure release, thereby suppressing the occurrence of structural defects (e.g., cracks and cracks) that occur when pressure is released. Therefore, fine voids and cracks, which are the starting points for characteristic deterioration due to external stress and thermal cycling, are reduced, resulting in a highly reliable solid electrolyte layer and / or electrode layer. This makes it possible to realize a battery 1000 with good performance and excellent reliability. Note that the softness of halogenated oxide B and halogenated oxide A can be compared by evaluation using a method such as micro-Vickers.

[0069] The solid electrolyte A may contain a crystalline phase represented by the following composition formula (7): Li2M2F6 Formula (7)

[0070] As a result, for example, when the halogenated oxide A contains a crystalline phase represented by the above composition formula (1): Li3AlX36, a solid electrolyte A softer than the halogenated oxide A can be obtained.

[0071] The solid electrolyte A may contain a crystalline phase represented by the following composition formula (8): Li2TiF6 Formula (8)

[0072] This allows for the production of a solid electrolyte A having ionic conductivity (e.g., ionic conductivity exceeding 1 μS / cm) comparable to that of the halogenated oxide A containing the crystalline phase represented by the composition formula (1): LiAlX36. This also allows for the production of a solid electrolyte A that is stable in the atmosphere. This allows for the production of a solid electrolyte A that has high ionic conductivity and high reliability. This allows for the production of a battery with excellent performance and reliability.

[0073] The halogenated oxide B may contain an amorphous portion B. This can impart softness to the halogenated oxide B, thereby improving the densification of the solid electrolyte A and the adhesion between particles. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (e.g., thermal stress), resulting in a battery 1000 with excellent performance and reliability.

[0074] The amorphous portion B may have a composition represented by the following composition formula (6): Li2M2(X2 1-b O b / 2 )6...Formula (6)

[0075] In the composition formula (6), b satisfies 0<b<1.

[0076] Therefore, the halogenated oxide B can be regarded as a composite material containing a soft material and a hard material. Therefore, while improving densification and interparticle binding, the effect of the halogenated oxide B can further improve mechanical strength. Therefore, a battery 1000 with higher reliability can be obtained.

[0077] In the amorphous portion B, M2 may contain Ti. This allows the solid electrolyte A to have atmospheric stability, high-temperature durability up to about 700°C, and high ionic conductivity of, for example, 1 μS / cm or more. As a result, a more reliable battery can be obtained.

[0078] The halide oxide B may further contain at least one element selected from the group consisting of Na, K, P, Si, Zr, and Nb. These elements act as auxiliary agents that promote the solid-state reaction when synthesizing the halide oxide B, thereby lowering the solid-state reaction temperature of the halide oxide B and homogenizing the reaction state. This reduces deviation from the desired composition of the halide oxide B due to evaporation of the constituent components, and reduces compositional variation. As a result, a solid electrolyte A is obtained that has excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength.

[0079] The content of solid electrolyte A may be, for example, 0.01 vol % or more and 5 vol % or less in solid electrolyte layer 300, and may be, for example, 0.01 vol % or more and 3 vol % or less in first electrode layer 100. Such a content of solid electrolyte A can be confirmed by elemental analysis using a high-resolution composition map such as EPMA of a cross section treated by ion polishing or the like.

[0080] The solid electrolyte A may be dispersed in the solid electrolyte layer 300 and / or the electrode layer, and may be present between the solid electrolyte particles and / or the active material particles or in the voids, or may be contained in the solid electrolyte layer 300 and / or the electrode layer in another form.

[0081] For example, a coating layer that covers at least a portion of the surface of the solid electrolyte particles and / or the active material particles may contain the solid electrolyte A. This enhances the mechanical bonding between the solid electrolyte particles and / or the active material particles (i.e., the anchor effect), improving the reliability of the battery 1000 against external stress, thermal cycles, and the like of the solid electrolyte layer 300 and / or the electrode layer.

[0082] When at least one selected from the group consisting of the first electrode layer 100 and the second electrode layer 200 includes active material particles and a coating layer that covers at least a portion of the surface of the active material particles, the coating layer may contain solid electrolyte A. This configuration can enhance the binding and mechanical bonding between the active material particles (i.e., the anchor effect). This improves the strength of the electrode layer against external stress and thermal cycles, thereby suppressing the occurrence of structural defects such as cracks in the electrode layer. This can further improve the reliability of the battery 1000.

[0083] The presence of solid electrolyte A in battery 1000 can be determined by EPMA, EDS, and X-ray fluorescence spectroscopy (XRF). The morphology and composition can be analyzed by composition analysis (point analysis or area analysis) using EPMA, EDS, etc. of a polished cross section processed with an ion polisher or the like.

[0084] In this way, by incorporating solid electrolyte A into the solid electrolyte layer 300 and / or the electrode layers, which are prone to structural defects due to external impacts, charge / discharge cycles, and thermal cycles, structural defects and deterioration of material properties can be suppressed, thereby reducing deterioration of the properties of the solid electrolyte layer 300 and / or the electrode layers, and realizing a highly reliable battery 1000.

[0085] The softness of the solid electrolyte A may be adjusted depending on the purpose. For example, a combination of multiple types of solid electrolyte A may be used. This improves the mechanical strength of the battery 1000 and suppresses the occurrence of structural defects due to external impacts, charge / discharge cycles, and thermal cycles.

[0086] An example of the solid electrolyte A will be described in more detail below. In the following, the example of the solid electrolyte A will be described assuming that the halide oxide contained in the solid electrolyte A is a substance obtained by substituting part of the halogen element in the halide crystal with oxygen.

[0087] The solid electrolyte A is, for example, a halide oxide A (Li3M1(X1)) in which a part of the halogen element of each halide of Li3M1X16 and Li2M2X26 is substituted with oxygen in a halide containing a crystal phase of Li3M1X16 (halide A) and Li2M2X26 (halide B). 1-a O a / 2 ) 6, (0 < a < 1)) and halide oxide B (Li2M2(X2 1-b O b / 2 ) 6, (0<b<1)). For example, the particles 400 of solid electrolyte A may contain halide oxide A (Li3M1(X1 1-a O a / 2 ) 6, (0 < a < 1)) and halide oxide B (Li2M2(X2 1-b O b / 2 ) 6, (0<b<1)), in which case the relationship a ≥ b may be satisfied.

[0088] For example, Li3M1X16 may be Li3AlF6. Li2M2X26 may be Li2TiF6. From the viewpoint of mechanical strength, it is desirable that the oxygen substitution amount of Li3AlF6 is equal to or greater than Li2TiF6 (i.e., a ≥ b). In this way, by increasing the oxygen substitution amount of Li3AlF6, which has a high melting point and is hard, a solid electrolyte A containing a harder halogenated oxide A is formed. By including such a solid electrolyte A in the solid electrolyte layer 300 and / or electrode layer, the battery 1000 can have increased mechanical strength and further improved reliability. The oxygen substitution amount in the halogenated oxide is, for example, 0.01 atomic % to 50 atomic %. It is desirable to synthesize the solid electrolyte A by adjusting the oxygen substitution amount in consideration of the desired ionic conductivity and hardness of the solid electrolyte A particles 400. The oxygen substitution amount can be estimated by detecting oxygen elements in solid electrolyte A through elemental analysis using, for example, an electron probe microanalyzer (EPMA) or energy dispersive X-ray spectroscopy (EDS). Crystal phases (e.g., LiAlF and LiTiF) can be confirmed by powder X-ray diffraction (powder XRD), micro-area X-ray diffraction (micro-area XRD), or high-resolution transmission electron microscope (TEM) observation. Furthermore, the oxygen substitution amount of each crystalline phase (e.g., LiAlF and LiTiF) can also be determined by quantitatively evaluating the oxygen substitution amount using EPMA or EDS. Furthermore, the LiTiF phase, which has a lower melting point, is softer than the LiAlF phase. Therefore, by incorporating a halogenated oxide in which the halogen element in the halide crystal phase is substituted with oxygen, together with the LiTiF phase, into the solid electrolyte layer 300 and / or the electrode layer, the adhesiveness of the solid electrolyte layer 300 and / or the electrode layer can be improved. This can suppress the occurrence of structural defects (e.g., interlayer or intralayer delamination and cracks) in the solid electrolyte layer 300 and / or the electrode layer due to expansion and contraction of the electrode layer caused by charge / discharge and thermal cycling. Furthermore, by incorporating a halogenated oxide A in which LiM1X16 is partially substituted with oxygen into the solid electrolyte layer 300 and / or the electrode layer, the mechanical reliability of the battery is improved.For this reason, depending on the application, if practical reliability is sufficient for stress absorption in thermal cycles and the like, it is possible to use only halogenated oxide A without including halogenated oxide B, which is a relatively soft Li2M2X26 in which some of the halogen elements have been substituted with oxygen. In other words, it is not necessary to include halogenated oxide B. The hardness and softness of each part or particle can be comparatively evaluated using a micro-Vickers device.

[0089] Furthermore, the solid electrolyte layer 300 and / or the electrode layer may contain a solid electrolyte A containing a LiAlF phase, which is a combination of orthorhombic and monoclinic crystal structures. This allows for a wider range of adjustment of mechanical strength, heat resistance, and binding properties by controlling the ratio of these crystal systems. Furthermore, composite particles (containing two crystal systems) containing an orthorhombic (surface layer) and a monoclinic (inner) crystal structure within a single particle can also be used. This allows for a more dispersed orientation of the particle characteristics, resulting in further improvements in mechanical strength, heat resistance, and binding properties. Furthermore, the inclusion of amorphous portions (i.e., unordered, non-oriented, and soft portions) disperses and absorbs stress, further improving reliability.

[0090] With the above-described configuration, the reliability of the battery 1000 can be improved by the hardness of the particles 400 of the solid electrolyte A containing the halogenated oxide A, the improved anchoring effect of the hard particles with the surroundings, and the densification and stress absorption effect of the relatively soft particles.

[0091] The halogenated oxide A of the solid electrolyte A can be, for example, a monoclinic or orthorhombic LiAlF phase in which some of the halogen elements (i.e., F) are substituted with oxygen. The LiAlF phase may be a composition in which LiAlF contains, for example, Ti, Na, Ca, Si, Zr, and Ga. These elements act as reaction accelerators for the synthesis, allowing the synthesis temperature to be lowered. Furthermore, these elements can control the content ratio of the monoclinic or orthorhombic phase.

[0092] A halogenated oxide A containing a phase in which part of the F in the orthorhombic LiAlF phase is substituted with oxygen has excellent high-temperature stability (e.g., stability at 400°C to 1000°C) and is hard, thereby improving mechanical strength and heat resistance. Generally, organic binders used in all-solid-state batteries formed by a powder compaction process, such as sulfide-based solid electrolytes, rapidly soften at temperatures above the glass transition point of the organic binder, e.g., 100°C to 250°C. Therefore, by incorporating a solid electrolyte A containing a halogenated oxide A containing a phase in which part of the F in the orthorhombic LiAlF phase is substituted with oxygen, into the solid electrolyte layer 300 and / or electrode layer, a decrease in the mechanical strength of the battery 1000 at high temperatures (e.g., 100°C or higher) can be suppressed. On the other hand, halogenated oxide A containing a monoclinic LiAlF phase in which part of the F is substituted with oxygen is softer than halogenated oxide A containing an orthorhombic LiAlF phase in which part of the F is substituted with oxygen. Therefore, by incorporating halogenated oxide A containing a monoclinic LiAlF phase in which part of the F is substituted with oxygen into the solid electrolyte layer 300 and / or the electrode layer, the bonding strength of the solid electrolyte layer 300 and / or the electrode layer can be improved. This can suppress the occurrence of structural defects (e.g., interlayer or intralayer peeling and cracking) in the solid electrolyte layer 300 and / or the electrode layer due to expansion and contraction of the electrode layer caused by charge / discharge and thermal cycles. A solid electrolyte A containing a multi-crystal phase combining the above-described orthorhombic and monoclinic systems in the LiAlF phase, in which some of the F in the LiAlF phase is substituted with oxygen, may be included in the solid electrolyte layer 300 and / or electrode layer. This allows the mechanical strength, heat resistance, and binding properties of the battery 1000 to be adjusted over a wide range by controlling the ratio of the crystal systems of the halogenated oxides contained in the solid electrolyte A. Also, composite particles (composite particles containing two crystal systems) containing an orthorhombic system (e.g., a surface layer) and a monoclinic system (e.g., an interior) in a single particle can be used. This provides the effect of improving mechanical strength, heat resistance, and binding properties at the particle level.Furthermore, a halogenated oxide B, for example, a phase in which part of the tetragonal F in the tetragonal Li2TiF6 phase is substituted with oxygen, can also be used as one component of the composite particles. Thus, composite particles having different crystal structures of halogenated oxide A and halogenated oxide B can achieve better dispersion of particle orientation (due to the different crystal structures), thereby improving mechanical strength, heat resistance, and binding properties. Therefore, for example, composite particles of a phase in which part of the F in the orthorhombic Li3AlF6 phase is substituted with oxygen and a phase in which part of the F in the tetragonal Li2TiF6 phase is substituted with oxygen, or a phase in which part of the F in the orthorhombic and monoclinic Li3AlF6 phase is substituted with oxygen and a phase in which part of the F in the tetragonal Li2TiF6 phase is substituted with oxygen, are preferred in terms of the effectiveness of the battery of the present disclosure. Furthermore, it is even more preferred to include an amorphous component (disordered, non-directional, soft, and stress-absorbing) in the composite particles.

[0093] Furthermore, part of the granulated solid electrolyte and / or active material particles (aggregates of a plurality of particles) may be coated with solid electrolyte A. This makes it possible to suppress external stress on the particles coated with solid electrolyte A, and stress acting on the particles coated with solid electrolyte A due to charge / discharge or thermal cycling.

[0094] In this way, by dispersing and incorporating the particles 400 of solid electrolyte A in areas where structural defects are likely to occur due to external stress, charge / discharge, or thermal cycling, structural defects and deterioration of material properties can be suppressed, thereby reducing deterioration of the properties of the solid electrolyte layer 300 and / or the electrode layers, and realizing a highly reliable battery.

[0095] It is desirable to adjust the softness and hardness of the particles 400 of solid electrolyte A depending on the purpose. For example, M1 may be at least one selected from the group consisting of B, Al, and Ga. For example, M2 may be at least one selected from the group consisting of Ti, Sn, and Zr. M1, M2, and the halogen element may each contain multiple elements.

[0096] This allows the physical properties (e.g., hardness and heat resistance) of the solid electrolyte A to be adjusted over a wide range, thereby improving mechanical strength and suppressing the occurrence of structural defects associated with external stress, charge / discharge, or thermal cycling. For example, a halide solid electrolyte may be used for the solid electrolyte layer 300 and the electrode layer composite. Halides generally tend to have a higher thermal expansion coefficient than other compounds such as oxides. In this way, a configuration in which the thermal expansion difference between adjacent materials is large is likely to result in structural defects such as interfacial peeling and cracking. To prevent such problems, it is desirable to include a halide in both the solid electrolyte material and the halide oxide contained in the solid electrolyte A. Furthermore, it is preferable to include a common type of halogen element. Specifically, for a halide solid electrolyte, a solid electrolyte containing a halogen oxide in which the halogen element is partially substituted with oxygen is preferable. For example, for a halide solid electrolyte containing Li2AlF6-Li3TiF6, a halogen oxide in which the F element in these crystalline phases is partially substituted with oxygen is preferable.

[0097] As described above, solid electrolyte A may include two or more halide solid electrolytes and a halogenated oxide solid electrolyte in which some of the halogen atoms in the halide solid electrolytes have been replaced with oxygen. Furthermore, for example, solid electrolyte A may include, as the halide solid electrolyte, a halide solid electrolyte containing multiple M1 elements, such as Li, M1(Al, B, Ga)X, a halide solid electrolyte containing multiple M2 elements, such as Li, M2(Ti, Sn, Zr)X, or a halide solid electrolyte containing multiple halogen elements (F, Cl, Br, and I), and a halogenated oxide solid electrolyte in which some of the halogen atoms in the halide solid electrolytes have been replaced with oxygen. By varying the mixing ratio of these elements in this manner, ionic conductivity, atmospheric stability, and high reliability (external stress, charge / discharge, and thermal cycling) can be controlled over a wide range depending on the application. This allows for the realization of a highly reliable battery. As described above, oxygen replacement of halides can be determined using EPMA or XRF. The state (shape) and composition can be analyzed by composition analysis (point analysis or area analysis) using EPMA, EDS, or the like on a polished cross section processed with an ion polisher or the like.

[0098] By using the solid electrolyte A having the above-described configuration, it is possible to prevent defects such as cracks from occurring in the internal structure of the battery due to external stress, thermal shock, charge / discharge, and charge / discharge thermal cycles.

[0099] (Solid Electrolyte B) As described above, the solid electrolyte B contains a halogenated oxide, and the halogenated oxide contains a halogenated oxide B composed of Li, M2, X2, and O.

[0100] The halogenated oxide in solid electrolyte B may further include a halogenated oxide A consisting of Li, M1, X1, and O. When the halogenated oxide in solid electrolyte B includes a halogenated oxide B and a halogenated oxide A, the ratio of the amount of O to the sum of the amounts of X2 and O in the halogenated oxide B (O / (X2+O)) may be greater than the ratio of the amount of O to the sum of the amounts of X1 and O in the halogenated oxide A (O / (X1+O)), i.e., the relationship O / (X1+O)<O / (X2+O) may be satisfied. For example, the characteristics of the halogenated oxide B and the halogenated oxide A can be controlled over a wide range by adjusting the content ratio of the halogenated oxide B and the halogenated oxide A, the type of halogen element constituting these halogenated oxides, and the oxygen content ratio. This enables control over a wider range to improve the battery characteristics and reliability. The ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)) can be regarded as the oxygen content in halogenated oxide B. The ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)) can be regarded as the oxygen content in halogenated oxide A.

[0101] For example, halide oxide B tends to have a lower melting point and be softer than halide oxide A. By increasing the oxygen content in halide oxide B relative to that in halide oxide A to harden halide oxide B, the effect of improving the impact resistance and thermal shock resistance of the battery by solid electrolyte B is more easily realized. Furthermore, by including halide oxide A, which is harder than halide oxide B, solid electrolyte B can be a composite material containing materials of different hardness, and the fracture limits of flexural strength and toughness can be dispersed. As a result, solid electrolyte B can produce a dense battery 1000 with excellent mechanical strength. Furthermore, since solid electrolyte B contains multiple materials with different compression characteristics, the deformation pressure is dispersed. Therefore, air is gradually expelled from the powder compact during the compression process, reducing the residual air trapped inside the powder compact and suppressing springback of the powder compact (i.e., expansion of the powder compact after pressure release). This improves the problem of cracks and fractures in the powder compact, thereby further improving the reliability of the battery 1000.

[0102] The solid electrolyte B may further contain a halide. Halides share a structure with halide oxides in that they contain a halogen element. Therefore, halides have a thermal expansion coefficient similar to that of halide oxides, good bondability, and good affinity with halide oxides. By including a halide in addition to a halide oxide in the solid electrolyte B, the battery 1000 according to the first embodiment is able to suppress the occurrence of structural defects (e.g., interfacial peeling between the solid electrolyte and the halide oxide, and the occurrence of cracks) due to charge / discharge cycles and thermal shock, thereby achieving high reliability.

[0103] The solid electrolyte B may further contain a halide B consisting of Li, M2, and X2. That is, the solid electrolyte B may contain a halide B containing elements common to the halide oxide B (i.e., Li, M1, and X1). The halide B has a thermal expansion coefficient close to that of the halide oxide B, good bonding properties, and good affinity with the halide oxide B. This allows for the production of a solid electrolyte B having high, excellent ionic conductivity of, for example, 1 μS / cm or more, and also having improved atmospheric stability. This makes it possible to obtain a battery 1000 with high reliability and excellent performance.

[0104] The solid electrolyte B may further contain a halide A consisting of Li, M1, and X1. That is, the solid electrolyte B may contain a halide A containing elements common to the halide oxide A (i.e., Li, M1, and X1). The halide A has a thermal expansion coefficient close to that of the halide oxide A, good bonding properties, and good affinity with the halide oxide A. As a result, when the solid electrolyte B contains the halide oxide A and the halide A, a solid electrolyte B having high, excellent ionic conductivity of, for example, 1 μS / cm or more and improved atmospheric stability can be obtained. Therefore, a battery 1000 with high reliability and excellent performance can be obtained.

[0105] The solid electrolyte B included in the battery 1000 according to the first embodiment may be particulate, such as the solid electrolyte B particles 400. When the solid electrolyte B is particulate, the solid electrolyte B can be included in the first electrode layer, the second electrode layer, and the solid electrolyte layer together with other solid electrolytes. For example, the solid electrolyte B can be included in the coating layer of the active material particles. That is, when the solid electrolyte B is included in the electrode layer and the solid electrolyte layer 300, the options for the form of the solid electrolyte B are expanded. Therefore, the desired components can be provided with impact resistance and thermal shock resistance at the microstructure level (e.g., the particle level). This allows for the realization of a highly reliable battery 1000. Furthermore, this configuration allows the battery of the present disclosure to be applied to all-solid-state batteries formed from a compact, such as those formed using sulfide-based solid electrolytes and halide-based solid electrolytes, which have excellent ionic conductivity. This allows for the realization of a highly reliable all-solid-state battery with excellent performance. Furthermore, for example, by using finely pulverized particles of solid electrolyte B (for example, particles having a particle diameter of 1 μm or less), the solid electrolyte layer 300 can be made thinner, and the coating layer of the active material particles or the like can be made thinner, thereby improving the capacity of the battery 1000.

[0106] The particles 400 of the solid electrolyte B are, for example, uniformly dispersed within the first electrode layer 100 and the solid electrolyte layer 300 .

[0107] The size of the particles 400 of solid electrolyte B can be appropriately selected depending on the first electrode layer 100 and solid electrolyte layer 300 containing the particles 400 (e.g., depending on the sizes of the active material particles and solid electrolyte particles), and may, for example, have an average particle diameter of 0.05 μm or more and 10 μm or less. In FIG. 1 , the particles 400 of solid electrolyte B are shown to have a spherical particle shape, but they may also have a particle shape other than a spherical shape, such as a scale shape.

[0108] The particle diameter of the solid electrolyte B particles 400 is preferably small. This allows the solid electrolyte B particles 400 to be uniformly dispersed throughout the first electrode layer 100 and the solid electrolyte layer 300. As a result, the surface area of ​​the solid electrolyte B increases, thereby increasing the bonding area between the solid electrolyte B particles 400 and the surrounding active material or solid electrolyte. Furthermore, fine pores are formed around the hard fine particles of solid electrolyte B, reducing the heat capacity and improving thermal shock resistance. Therefore, the mechanical reliability (flexural strength) and thermal shock resistance of the first electrode layer 100 and the solid electrolyte layer 300 are further improved by miniaturizing the solid electrolyte B particles 400 (for example, by miniaturizing the particle diameter to 1 μm or less).

[0109] The particles 400 of solid electrolyte B may contain a halogenated oxide and a halide. When the particles 400 of solid electrolyte B contain both a halide and a hard halogenated oxide, the adhesion between particles is improved. Therefore, for desired components, the effects of impact resistance and thermal shock resistance can be obtained at the microstructure level (e.g., particle level). In particular, the effects of improved adhesion between particles, improved strength, and improved thermal shock resistance can be obtained in a powder compact. This configuration results in a battery 1000 with excellent reliability.

[0110] The particles 400 of solid electrolyte B may contain an oxide halide. That is, the oxide halide may be present in the internal region of the particles 400 of solid electrolyte B. This results in the hard oxide halide being disposed inside the particles and a softer material, such as a halide, being disposed on the particle surface, thereby enhancing interparticle bonding and providing the hard core portion as a reinforcing material. Furthermore, the core portion of the particles has reduced plastic deformability, thereby achieving high particle bonding while suppressing densification. This results in high interparticle bonding, improved strength, and improved thermal shock resistance, particularly in a powder compact.

[0111] The volume fraction of the halogenated oxide in the particles 400 of solid electrolyte B increases, for example, as the volume of the particles 400 of solid electrolyte B increases. This allows the particles 400 of solid electrolyte B to be given softness (e.g., deformability) or hardness, which can be adjusted over a wide range by, for example, changing the particle size. Furthermore, since the gaps between the large, hard particles with a larger volume fraction of halogenated oxide are filled with small, soft particles with a smaller volume fraction of halogenated oxide, the bonding strength between the particles 400 of solid electrolyte B is further improved. Therefore, the bonding strength between the particles 400 of solid electrolyte B and the strength are improved, particularly in a compact.

[0112] The solid electrolyte B particle 400 may have multiple regions where a halide oxide is present. This allows the softness (e.g., deformability) or hardness of the solid electrolyte B particle 400 to be adjusted over a wider range. This improves the reliability of the battery 1000 against external stresses and thermal cycles. The softness or hardness of the solid electrolyte B particle 400 can be adjusted by adjusting the size and number of the regions where a halide oxide is present. Such particles having multiple regions where a halide oxide is present within the particle can be formed, for example, by mixing a halide oxide powder obtained by halogenating an oxide with a halide solid electrolyte by a mechanochemical method to form composite particles. Furthermore, particles having multiple regions where a halide oxide is present within the particle can also be formed by oxidizing a halide having a scale-like or needle-like shape.

[0113] In the halogenated oxide B, M2 may contain Ti. This allows the solid electrolyte B to have high ionic conductivity, for example, of 1 μS / cm or more, and high heat resistance due to having a melting point, for example, of 700° C. or more. This makes it possible to obtain a battery 1000 with even better performance and heat resistance. In addition, in this case, by increasing the oxygen content in the halogenated oxide B, the heat resistance and hardness of the solid electrolyte B are further improved, thereby further improving the reliability of the battery 1000.

[0114] In the halogenated oxide B, X2 may contain F. By including F in the halogenated oxide B, the solid electrolyte B containing the halogenated oxide B can have high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 700°C or more. Therefore, a battery with higher reliability can be obtained. Note that the excellent atmospheric stability here means, for example, excellent durability against normal atmospheric moisture.

[0115] In the halogenated oxide A, M1 may contain Al. This allows the solid electrolyte B to have high ionic conductivity, for example, of 1 μS / cm or more. Furthermore, when M1 in the halogenated oxide A contains Al, the melting point of the halogenated oxide A increases and the halogenated oxide A becomes harder. This allows the solid electrolyte B to have high impact resistance. Therefore, a battery with even better performance and impact resistance can be obtained. The ionic conductivity derived from the halogenated oxide A decreases with an increase in the oxygen content in the halogenated oxide A. Therefore, to further improve the ionic conductivity, the oxygen content in the halogenated oxide A is limited. For example, by making the oxygen content smaller than that of the halogenated oxide B, the halogenated oxide A can have higher ionic conductivity than the halogenated oxide B.

[0116] In the halogenated oxide A, X1 may contain F. By including F in the halogenated oxide A, the solid electrolyte B containing the halogenated oxide A can have high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 700°C or more. Therefore, a battery with higher reliability can be obtained. Here, excellent atmospheric stability means, for example, excellent durability against normal atmospheric moisture.

[0117] The halide oxide contained in the solid electrolyte B may contain at least one element selected from the group consisting of Na, K, Ca, Si, Zr, Ga, P, and Nb. These elements act as auxiliary agents to promote the solid-state reaction during the synthesis of the halide oxide, thereby lowering the solid-state reaction temperature of the halide oxide and homogenizing the reaction state. This reduces the deviation from the desired composition due to evaporation of the constituent components and the compositional variation of the halide oxide. Therefore, a solid electrolyte B with excellent properties can be obtained. Furthermore, the inclusion of these elements prevents the halide oxide from sintering too hard, making it easier to pulverize the halide oxide and enabling fine pulverization (e.g., into particles with a particle size of 1 μm or less). This increases the surface area of ​​the halide oxide, further enhancing the effects of the solid electrolyte B (e.g., its function as a reinforcing material and an anchor material between particles, and its improved thermal shock resistance). Furthermore, the halide oxide can be incorporated into thin-layer batteries.

[0118] The solid electrolyte B may contain a crystalline phase represented by the following composition formula (3): Li2TiX46 Formula (3)

[0119] In the composition formula (3), X4 is at least one selected from the group consisting of F, Cl, Br, and I.

[0120] This provides the solid electrolyte layer B with high ionic conductivity, for example, 1 μS / cm or more, and high reliability, thereby making it possible to obtain a battery with even greater reliability.

[0121] The solid electrolyte B may contain a crystalline phase represented by the following composition formula (4): Li2TiF6 Formula (4)

[0122] This allows the solid electrolyte layer B to have further atmospheric stability. Therefore, fluctuations in the properties of the solid electrolyte layer B during the manufacturing process can be suppressed, making it possible to reproducibly obtain desired properties. Furthermore, strict dew point environmental control (i.e., temperature and humidity control) during the manufacturing process is no longer necessary, thereby reducing the manufacturing cost of the battery.

[0123] The halogenated oxide B may contain an amorphous portion B. This can impart softness to the halogenated oxide B, thereby improving the densification of the solid electrolyte B and the adhesion between particles. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (e.g., thermal stress), resulting in a battery 1000 with excellent performance and reliability.

[0124] The amorphous portion B may have a composition represented by the following composition formula (6): Li2M2(X2 1-b O b / 2 )6...Formula (6)

[0125] In the composition formula (6), b satisfies 0<b<1.

[0126] Therefore, the halogenated oxide B can be regarded as a composite material containing a soft material and a hard material. Therefore, while improving densification and interparticle binding, the effect of the halogenated oxide B can further improve mechanical strength. Therefore, a battery 1000 with higher reliability can be obtained.

[0127] In the amorphous portion B, M2 may contain Ti. This allows the solid electrolyte B to have atmospheric stability, high-temperature durability up to about 700°C, and high ionic conductivity of, for example, 1 μS / cm or more. As a result, a more reliable battery 1000 can be obtained.

[0128] The halide oxide B may further contain at least one element selected from the group consisting of Na, K, P, Si, Zr, and Na. These elements act as auxiliary agents that promote the solid-state reaction when synthesizing the halide oxide B, thereby lowering the solid-state reaction temperature of the halide oxide B and homogenizing the reaction state. This reduces deviation from the desired composition of the halide oxide B due to evaporation of the constituent components, and reduces compositional variation. As a result, a solid electrolyte B having excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength, can be obtained.

[0129] The halogenated oxide A may have a higher melting point than the halogenated oxide B. When the halogenated oxide A has a higher melting point than the halogenated oxide B, the halogenated oxide A is usually harder than the halogenated oxide B. Therefore, for example, when the solid electrolyte B is contained in the solid electrolyte layer and / or the electrode layer, the halogenated oxide A can suppress plastic deformation and packing progress of the solid electrolyte layer and / or the electrode layer. Because the halogenated oxide A has a high melting point, it can maintain the particle shape and particle characteristics even against heat generated by particle friction during compact formation under pressure. This suppresses densification of the solid electrolyte layer and / or the electrode layer, increasing the number of pores and lowering the density. Furthermore, the hardness of the halogenated oxide A creates a strong anchoring effect between the halogenated oxide A and the halogenated oxide B, forming many pores around it. This lowering of the density reduces the heat capacity, thereby reducing cracks in the solid electrolyte layer and / or the electrode layer caused by thermal cycling and rapid temperature changes. Therefore, a highly reliable solid electrolyte layer and / or electrode layer can be obtained. Due to these effects, a battery 1000 with good performance and excellent reliability can be realized.

[0130] The halogenated oxide A may be harder than the halogenated oxide B. For example, when the solid electrolyte B is included in the solid electrolyte layer and / or electrode layer, the densification of the solid electrolyte layer and / or electrode layer is suppressed, the number of pores increases, and the density decreases. Furthermore, the hardness of the halogenated oxide A creates a strong anchoring effect between the halogenated oxide A and the halogenated oxide B, forming many pores around the halogenated oxide A. This lower density reduces the heat capacity, thereby reducing cracks in the solid electrolyte layer and / or electrode layer that occur due to thermal cycling and rapid temperature changes. Therefore, a highly reliable solid electrolyte layer and / or electrode layer can be obtained. These effects enable the realization of a battery 1000 with excellent performance and reliability. The softness of the halogenated oxide A and the halogenated oxide B can be compared using a method such as micro-Vickers.

[0131] The solid electrolyte B may contain a crystalline phase represented by the following composition formula (9): Li3M1F6 Formula (9)

[0132] As a result, for example, when the halide oxide B contains a crystalline phase represented by the above composition formula (3): Li2TiX46, a solid electrolyte B harder than the halide oxide B can be obtained.

[0133] The solid electrolyte B may contain a crystalline phase represented by the following composition formula (10): LiAlF Formula (10)

[0134] This allows for the production of a solid electrolyte B having ionic conductivity (e.g., ionic conductivity exceeding 1 μS / cm) equal to or greater than that of the halide oxide B containing the crystalline phase represented by the composition formula (3): LiTiX46. This also allows for the production of a solid electrolyte B that is stable in the atmosphere and at high temperatures. This allows for the production of a solid electrolyte B that has high ionic conductivity and high reliability. This allows for the production of a battery with excellent performance and reliability.

[0135] The halogenated oxide A may contain an amorphous portion A. This can impart softness to the halogenated oxide A, thereby improving the densification of the solid electrolyte B and the adhesion between particles. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (e.g., thermal stress), resulting in a battery 1000 with excellent performance and reliability.

[0136] The amorphous portion A may have a composition represented by the following composition formula (5): Li3M1(X1 1-a O a / 2 )6...Formula (5)

[0137] In the composition formula (5), a satisfies 0<a<1.

[0138] Therefore, the halogenated oxide A can be regarded as a composite material containing a soft material and a hard material. Therefore, the mechanical strength can be further improved by the effect of the halogenated oxide A while improving densification and interparticle binding. Therefore, a battery 1000 with higher reliability can be obtained.

[0139] In the amorphous portion A, M1 may contain Al. This allows the solid electrolyte B to have atmospheric stability, high-temperature durability up to about 800°C, and high ionic conductivity of, for example, 1 μS / cm or more. As a result, a more reliable battery can be obtained.

[0140] The halogenated oxide A may further contain at least one element selected from the group consisting of Na, Ca, Si, Zr, and Ga. These elements act as auxiliary agents that promote the solid-state reaction when synthesizing the halogenated oxide A, thereby lowering the solid-state reaction temperature of the halogenated oxide A and homogenizing the reaction state. This reduces deviation from the desired composition of the halogenated oxide A due to evaporation of the constituent components, and reduces compositional variation. As a result, a solid electrolyte B having excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength, can be obtained.

[0141] The content of solid electrolyte B may be, for example, 0.01 vol % or more and 5 vol % or less in solid electrolyte layer 300, and may be, for example, 0.01 vol % or more and 3 vol % or less in first electrode layer 100. Such a content of solid electrolyte B can be confirmed by elemental analysis using a high-resolution composition map such as EPMA of a cross section treated by ion polishing or the like.

[0142] The solid electrolyte B may be dispersed in the solid electrolyte layer 300 and / or the electrode layer, and may be present between the solid electrolyte particles and / or the active material particles or in the voids, or may be contained in the solid electrolyte layer 300 and / or the electrode layer in another form.

[0143] For example, a coating layer that covers at least a portion of the surface of the solid electrolyte particles and / or the active material particles may contain solid electrolyte B. This enhances the mechanical bonding between the solid electrolyte particles and / or the active material particles (i.e., anchor effect), improving the reliability of the battery 1000 against external stress, thermal cycles, and the like on the solid electrolyte layer 300 and / or the electrode layer.

[0144] When at least one selected from the group consisting of the first electrode layer 100 and the second electrode layer 200 includes active material particles and a coating layer that covers at least a portion of the surface of the active material particles, the coating layer may contain solid electrolyte B. This configuration can enhance the binding and mechanical bonding between the active material particles (i.e., the anchor effect). This improves the strength of the electrode layer against external stress and thermal cycles, and can suppress the occurrence of structural defects such as cracks in the electrode layer. This can further improve the reliability of the battery 1000.

[0145] The presence of solid electrolyte B in battery 1000 can be determined by EPMA, EDS, and XRF. The morphology and composition can be analyzed by composition analysis (point analysis or area analysis) using EPMA, EDS, etc. of a polished cross section processed with an ion polisher or the like.

[0146] In this way, by incorporating solid electrolyte B into the solid electrolyte layer 300 and / or the electrode layers, which are prone to structural defects due to external impacts, charge / discharge cycles, and thermal cycles, structural defects and deterioration of material properties can be suppressed, thereby reducing deterioration of the properties of the solid electrolyte layer 300 and / or the electrode layers, and realizing a highly reliable battery 1000.

[0147] The softness of the solid electrolyte B may be adjusted depending on the purpose. For example, a combination of multiple types of solid electrolytes B may be used. This improves the mechanical strength of the battery 1000 and suppresses the occurrence of structural defects due to external impacts, charge / discharge cycles, and thermal cycles.

[0148] An example of solid electrolyte B will be described in more detail below. In the following, the example of solid electrolyte B will be described assuming that the halide oxide contained in solid electrolyte B is a substance obtained by substituting part of the halogen element in halide crystal with oxygen.

[0149] The solid electrolyte B is, for example, a halide containing a crystal phase of Li2M2X26 (halide B) and Li3M1X16 (halide A), in which a part of the halogen element of each halide of Li2M2X26 and Li3M1X16 is substituted with oxygen, to form a halide oxide B (Li2M2(X2 1-b O b / 2 ) 6, (0<b<1)) and halide oxide A (Li3M1(X1 1-a O a / 2 ) 6, (0<a<1)). For example, the particles 400 of the solid electrolyte B may contain halide oxide B (LiM(X2 1-b O b / 2 ) 6, (0<b<1)) and halide oxide A (Li3M1(X1 1-a O a / 2 ) 6, (0<a<1)), in which case the relationship b>a may be satisfied.

[0150] For example, Li2M2X26 may be Li2TiF6. Li3M1X16 may be Li3AlF6. From the viewpoint of mechanical strength and thermal shock resistance, it is desirable that the oxygen substitution amount of Li2TiF6 be greater than that of Li3AlF6 (i.e., b > a). Increasing the oxygen substitution amount of Li2TiF6, which has a low melting point and is soft, increases the pores around the solid electrolyte B and reduces the heat capacity. By including such a solid electrolyte B in the solid electrolyte layer 300 and / or electrode layer, the battery 1000 can improve its thermal shock resistance, impact resistance, and flexural strength, thereby further improving its reliability. The oxygen substitution amount in the halide oxide is, for example, 0.01 atomic % to 50 atomic %. It is desirable to synthesize the solid electrolyte B by adjusting the oxygen substitution amount in consideration of the desired ionic conductivity and hardness of the particles 400. The oxygen substitution amount can be estimated by detecting oxygen elements in solid electrolyte B through elemental analysis such as EPMA or EDS. Crystal phases (e.g., Li2TiF6 phase and Li3AlF6 phase) can be confirmed by powder XRD, micro-XRD, and TEM observation. Furthermore, the oxygen substitution amount of each crystal phase (e.g., Li2TiF6 phase and Li3AlF6 phase) can be determined by quantitatively evaluating the oxygen substitution amount using EPMA or EDS. The Li3AlF6 phase, which has a higher melting point, is harder than the Li2TiF6 phase. Therefore, by incorporating the Li3AlF6 phase, as well as the Li2TiF6 phase, and also a halogenated oxide in which the halogen element in the crystal phase of halide A is substituted with oxygen, into the solid electrolyte layer 300 and / or electrode layer, the porosity of the solid electrolyte layer 300 and / or electrode layer is increased, further reducing the heat capacity, thereby achieving the effect of further improving thermal shock resistance. Therefore, the occurrence of structural defects (e.g., interlayer or intralayer peeling and cracking) in the solid electrolyte layer 300 and / or the electrode layer due to thermal shock and thermal cycling can be suppressed. Note that the inclusion of halogenated oxide B, in which LiM2X26 is partially substituted with oxygen, in the solid electrolyte layer 300 and / or the electrode layer improves the thermal shock resistance and mechanical reliability of the battery.For this reason, depending on the application, if practical reliability is sufficient in terms of thermal shock resistance and mechanical reliability, it is possible to use only halogenated oxide B without including halogenated oxide A, in which some of the halogen elements in the relatively hard Li3M1X16 are substituted with oxygen. In other words, it is not necessary to include halogenated oxide A. The hardness and softness of each part or particle can be compared and evaluated using a micro-Vickers device.

[0151] Furthermore, the solid electrolyte layer 300 and / or the electrode layer may contain a solid electrolyte B containing a LiAlF phase, which is a combination of orthorhombic and monoclinic crystal structures in the crystalline structure of the halogenated oxide A. This allows the mechanical strength, heat resistance, and binding ability to be adjusted over a wide range by controlling the ratio of these crystal systems. Furthermore, composite particles (containing two crystal systems) containing an orthorhombic crystal system (surface layer) and a monoclinic crystal system (interior layer) within a single particle can also be used. This allows for a more dispersed orientation of the particle characteristics, thereby improving the mechanical strength, heat resistance, and binding ability.

[0152] The above-described configuration can improve the reliability of the battery 1000.

[0153] The halogenated oxide A may be, for example, a monoclinic or orthorhombic LiAlF phase in which some of the halogen elements (i.e., F) have been replaced with oxygen. The LiAlF phase may be a composition containing, for example, Ti, Na, Ca, Si, Zr, and Ga in LiAlF. These elements act as reaction accelerators for the synthesis, lowering the synthesis temperature. Furthermore, these elements can control the content ratio of the monoclinic or orthorhombic phase.

[0154] Halide oxide A, which includes a phase in which part of the F in the orthorhombic LiAlF phase is substituted with oxygen, has excellent high-temperature stability (e.g., stability at 400°C to 1000°C) and is hard, thereby improving mechanical strength and heat resistance. Generally, organic binders used in all-solid-state batteries formed by a powder compaction process, such as sulfide-based solid electrolytes, rapidly soften at temperatures above the glass transition point of the organic binder, e.g., 100°C to 250°C. Therefore, by incorporating solid electrolyte B, which includes halide oxide A including a phase in which part of the F in the orthorhombic LiAlF phase is substituted with oxygen, into the solid electrolyte layer 300 and / or electrode layer, it is possible to suppress a decrease in the mechanical strength of the battery 1000 at high temperatures (e.g., 100°C or higher). On the other hand, halogenated oxide A containing a phase in which part of the F in the monoclinic LiAlF phase is substituted with oxygen is softer than halogenated oxide A containing a phase in which part of the F in the orthorhombic LiAlF phase is substituted with oxygen. Therefore, by incorporating halogenated oxide A containing a phase in which part of the F in the monoclinic LiAlF phase is substituted with oxygen into the solid electrolyte layer 300 and / or the electrode layer, the bonding strength of the solid electrolyte layer 300 and / or the electrode layer can be improved. This can suppress the occurrence of structural defects (e.g., interlayer or intralayer peeling and cracking) in the solid electrolyte layer 300 and / or the electrode layer due to expansion and contraction of the electrode layer caused by charge / discharge and thermal cycles. A solid electrolyte B containing a multi-crystal phase combining the above-described orthorhombic and monoclinic systems in the LiAlF phase, in which some of the F in the LiAlF phase is replaced with oxygen, may be included in the solid electrolyte layer 300 and / or electrode layer. This allows the mechanical strength, heat resistance, and binding properties of the battery 1000 to be adjusted over a wide range by controlling the ratio of the crystal systems of the halides contained in the solid electrolyte A. Furthermore, composite particles (composite particles containing two crystal systems) containing an orthorhombic system (e.g., a surface layer) and a monoclinic system (e.g., an interior) in a single particle can also be used. This provides the effect of improving mechanical strength, heat resistance, and binding properties.As described above, composite particles having different crystal structures, namely, halogenated oxide B (for example, a phase in which part of F in tetragonal Li2TiF6 phase is substituted with oxygen) and halogenated oxide A (for example, a phase in which part of F in orthorhombic and monoclinic Li3AlF6 phase is substituted with oxygen), have a more dispersed orientation of particle properties (because they are composed of different crystal structures), and therefore, can achieve the effect of improving mechanical strength, heat resistance, and binding ability. Therefore, for example, composite particles of a phase in which part of the F in the tetragonal Li2TiF6 phase is replaced with oxygen and a phase in which part of the F in the orthorhombic Li3AlF6 phase is replaced with oxygen, or a phase in which part of the F in the tetragonal Li2TiF6 phase is replaced with oxygen and a phase in which part of the F in the orthorhombic and monoclinic Li3AlF6 phase is replaced with oxygen are preferred in terms of the effects of the battery of the present disclosure, and further, it is more preferable to include an amorphous component (disordered, non-directional, soft, and stress-absorbing) as the composite particle. These crystalline phases can be evaluated by XRD, and the crystalline structure of the composite particles can be evaluated by particle observation using, for example, a high-resolution TEM.

[0155] Furthermore, part of the granulated solid electrolyte and / or active material particles (aggregates of a plurality of particles) may be coated with solid electrolyte B. This makes it possible to suppress external stress on the particles coated with solid electrolyte B, and stress acting on the particles coated with solid electrolyte B due to charge / discharge or thermal cycling.

[0156] In this way, by dispersing and incorporating the particles 400 of solid electrolyte B in areas where structural defects are likely to occur due to external stress, charge / discharge, or thermal cycling, structural defects and deterioration of material properties can be suppressed, thereby reducing deterioration of the properties of the solid electrolyte layer 300 and / or the electrode layers, and realizing a highly reliable battery.

[0157] It is desirable to adjust the softness and hardness of the particles 400 of solid electrolyte B depending on the purpose. For example, M1 may be at least one selected from the group consisting of B, Al, and Ga. For example, M2 may be at least one selected from the group consisting of Ti, Sn, and Zr. M1, M2, and the halogen element may each contain multiple elements.

[0158] This allows the physical properties of solid electrolyte B (e.g., hardness and heat resistance) to be adjusted over a wide range, improving mechanical strength and suppressing the occurrence of structural defects associated with external stress, charge / discharge, or thermal cycling. For example, a halide solid electrolyte may be used for the solid electrolyte layer 300 and the electrode layer composite. Halides generally tend to have a higher thermal expansion coefficient than other compounds such as oxides. In this manner, a configuration in which the thermal expansion difference between adjacent materials is large is likely to result in structural defects such as interfacial peeling and cracking. To prevent such problems, it is desirable for both the solid electrolyte material and the halide oxide contained in solid electrolyte B to contain a halide. Alternatively, a configuration in which halides contact each other may be included. It is also preferable for the halogen element contained in the solid electrolyte material and the halogen element contained in solid electrolyte B to be the same. For example, for a halide solid electrolyte containing Li2TiF6-Li3AlF6, a halogen oxide in which the F element in these crystalline phases is partially substituted with oxygen is preferable.

[0159] As described above, solid electrolyte B may be a mixture of two or more halide solid electrolytes and a halogenated oxide solid electrolyte in which the halogenated oxide is substituted with oxygen. For example, halide B may include a halide solid electrolyte of Li, M2(Ti, Sn, Zr)X2, and may further include a halide solid electrolyte containing Li, M1(B, Al, Ga)X1 and a halogenated oxide solid electrolyte in which some of the halogens in the halide solid electrolyte are substituted with oxygen. By varying the mixing ratio of these, ionic conductivity and high reliability (external stress, charge / discharge, and thermal cycling) can be controlled over a wide range depending on the application. This allows for the realization of a highly reliable battery. As described above, oxygen substitution of the halide can be determined using EPMA or XRF. Furthermore, the state (morphology) and composition of the halide can be analyzed by composition analysis (point analysis or area analysis) using EPMA, EDS, etc. on a polished cross section processed with an ion polisher or the like.

[0160] By using the solid electrolyte B having the above-described structure, it is possible to prevent defects such as cracks from occurring in the internal structure of the battery due to external stress, thermal shock, charge / discharge, and charge / discharge thermal cycles.

[0161] (Current Collector) The current collector is formed of a conductive material. Examples of the material for the current collector include stainless steel, nickel (Ni), aluminum (Al), iron (Fe), titanium (Ti), copper (Cu), palladium (Pd), gold (Au), platinum (Pt), or an alloy of two or more of these. As the current collector, a foil, plate, or mesh made of these materials can be used.

[0162] The material of the current collector can be selected in consideration of the manufacturing process, the temperature and pressure used, the operating potential of the battery applied to the current collector, or electrical conductivity, and can also be selected according to the tensile strength or heat resistance required for the battery.

[0163] The current collector may be a high-strength electrolytic copper foil or a clad material in which foils of different metals are laminated.

[0164] The thickness of the current collector is, for example, 10 μm or more and 100 μm or less.

[0165] The surface of the current collector may be roughened to have irregularities in order to improve adhesion to the active material layer.

[0166] The surface of the current collector may be coated with an adhesive component such as an organic binder. Furthermore, insulating particles, conductive particles, or semiconducting particles may be attached to the surface of the current collector. This strengthens the bonding at the interface between the current collector and other layers (e.g., active material layers), thereby improving the mechanical and thermal reliability and cycle characteristics of the battery 1000.

[0167] (Active Material Layer) The first active material layer 120 is, for example, a positive electrode active material layer. The first active material layer 120 is located between the first current collector 110 and the solid electrolyte layer 300. The first active material layer 120 may be in contact with a major surface of the first current collector 110. The first active material layer 120 may be in contact with a major surface of the solid electrolyte layer 300.

[0168] The second active material layer 220 is, for example, a negative electrode active material layer. The second active material layer 220 is sandwiched between the second current collector 210 and the solid electrolyte layer 300. The second active material layer 220 may be in contact with a major surface of the second current collector 210. The second active material layer 220 may be in contact with a major surface of the solid electrolyte layer 300.

[0169] The positive electrode active material layer contains a positive electrode active material.

[0170] The positive electrode active material is a material in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or extracted into or from the crystalline structure at a potential higher than that of the negative electrode, and oxidation or reduction occurs accordingly. The type of the positive electrode active material can be appropriately selected depending on the type of battery, and known positive electrode active materials can be used.

[0171] The positive electrode active material is, for example, a compound containing lithium and a transition metal element, such as an oxide containing lithium and a transition metal element, or a phosphate compound containing lithium and a transition metal element.

[0172] An example of an oxide containing lithium and a transition metal element is LiNi x M 1-xExamples of the lithium-nickel composite oxide include lithium nickel composite oxides such as LiCoO2 (where M is at least one selected from the group consisting of Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo, and W, and 0<x≦1 is satisfied), layered oxides such as lithium cobalt oxide (LiCoO2) and lithium nickel oxide (LiNiO2), or lithium manganese oxides having a spinel structure (e.g., LiMn2O4, Li2MnO3, or LiMnO2).

[0173] An example of a phosphate compound containing lithium and a transition metal element is lithium iron phosphate (LiFePO4) having an olivine structure.

[0174] The positive electrode active material may be sulfur (S) or a sulfide such as lithium sulfide (LiS). In this case, the positive electrode active material particles may be coated with or may have lithium niobate (LiNbO) or the like added thereto.

[0175] The positive electrode active material may be made of only one of these materials, or a combination of two or more of these materials.

[0176] The positive electrode active material layer may contain solid electrolyte A. For example, when the positive electrode active material layer includes positive electrode active material particles and a coating layer covering at least a portion of the surface of the active material particles, the coating layer may contain solid electrolyte A. This allows the positive electrode active material and the solid electrolyte contained in the positive electrode to be firmly bonded due to the anchoring effect of solid electrolyte A containing halogenated oxide A, thereby increasing mechanical strength. This reduces the interfacial resistance between the positive electrode active material and the solid electrolyte contained in the positive electrode. Furthermore, heat generation due to Joule heat is reduced in the positive electrode, which is prone to heat generation during charge and discharge operations, thereby achieving high heat resistance. This results in a battery with excellent performance (e.g., charge and discharge characteristics and durability). Here, battery durability refers to, for example, the battery's cycle characteristics and high-temperature stability. Furthermore, the anchoring effect of solid electrolyte A can suppress the problem of interface peeling between the positive electrode active material and the solid electrolyte due to external stress or expansion and contraction of the positive electrode active material due to charge and discharge, or stress due to expansion and contraction due to thermal cycling.

[0177] As shown in FIG. 1, the solid electrolyte A contained in the positive electrode active material layer may be solid electrolyte A particles 400, and the solid electrolyte B may be solid electrolyte B particles 400.

[0178] To enhance lithium ion conductivity or electron conductivity, the positive electrode active material layer may contain, in addition to the positive electrode active material, a material other than the positive electrode active material and solid electrolyte A. That is, the positive electrode active material layer may be a mixture layer. Examples of such materials include inorganic solid electrolytes, solid electrolytes such as sulfide-based solid electrolytes, conductive additives such as acetylene black, or binding binders such as polyethylene oxide and polyvinylidene fluoride. The solid electrolyte may be, for example, a halide solid electrolyte. Examples of the halide solid electrolyte contained in the positive electrode active material layer are the same as the examples of the halide solid electrolyte contained in the solid electrolyte layer 300 described below.

[0179] By mixing the positive electrode active material with other additive materials such as a solid electrolyte in a predetermined ratio, the positive electrode active material layer can improve the ionic conductivity and electronic conductivity in the positive electrode active material layer.

[0180] The positive electrode active material layer may have a thickness of, for example, 5 μm or more and 300 μm or less.

[0181] The negative electrode active material layer contains a negative electrode active material.

[0182] The negative electrode active material layer is a layer mainly composed of a negative electrode material such as a negative electrode active material.

[0183] The negative electrode active material is a material in which metal ions such as lithium (Li) ions or magnesium (Mg) ions are inserted or extracted into or from the crystalline structure at a potential lower than that of the positive electrode, and oxidation or reduction occurs accordingly. The type of the negative electrode active material can be appropriately selected depending on the type of battery, and known negative electrode active materials can be used.

[0184] Examples of the negative electrode active material include carbon materials such as natural graphite, artificial graphite, graphite carbon fiber, and resin-baked carbon, or alloy-based materials mixed with a solid electrolyte. Examples of alloy-based materials include LiAl, LiZn, LiBi, LiCd, LiSb, LiSi, and Li.4.4 Pb, Li 4.4 Sn, Li 0.17 C, and lithium alloys such as LiC6, lithium titanate (Li4Ti5O 12 ), zinc oxide (ZnO), or silicon oxide (SiO x ) are metal oxides such as

[0185] The negative electrode active material may be made of only one of these materials, or a combination of two or more of these materials.

[0186] To enhance lithium ion conductivity or electron conductivity, the negative electrode active material layer may contain, in addition to the negative electrode active material, a material other than the negative electrode active material. Examples of such materials include solid electrolytes such as inorganic solid electrolytes and sulfide solid electrolytes, conductive additives such as acetylene black, or binders such as polyethylene oxide and polyvinylidene fluoride. The solid electrolyte may be, for example, a halide solid electrolyte. Examples of the halide solid electrolyte contained in the negative electrode active material layer are the same as the examples of the halide solid electrolyte contained in the solid electrolyte layer 300 described below.

[0187] The negative electrode active material layer may have a thickness of, for example, 5 μm or more and 300 μm or less.

[0188] The negative electrode active material layer may contain the solid electrolyte A or the solid electrolyte B, similarly to the above-described positive electrode active material layer.

[0189] (Solid Electrolyte Layer) The solid electrolyte layer 300 includes a solid electrolyte.

[0190] The solid electrolyte layer 300 includes, for example, a solid electrolyte as a main component. Here, the main component refers to the component that is contained in the solid electrolyte layer 300 in the largest amount by mass. As described above, the solid electrolyte layer 300 may include, for example, solid electrolyte A or solid electrolyte B. The solid electrolyte A is, for example, particles 400 of solid electrolyte A. The solid electrolyte B is, for example, particles 400 of solid electrolyte B.

[0191] The solid electrolyte may be any known ion-conductive solid electrolyte for batteries. For example, a solid electrolyte that conducts metal ions such as lithium ions or magnesium ions can be used as the solid electrolyte contained in the solid electrolyte layer 300.

[0192] As the solid electrolyte, a sulfide solid electrolyte, an oxide solid electrolyte, or a halide solid electrolyte can be used.

[0193] Examples of sulfide-based solid electrolytes include LiS-P2S5-based, LiS-SiS2-based, LiS-B2S3-based, LiS-GeS2-based, LiS-SiS2-LiI-based, LiS-SiS2-Li3PO4-based, LiS-Ge2S2-based, LiS-GeS2-P2S5-based, and LiS-GeS2-ZnS-based.

[0194] The oxide-based solid electrolyte is, for example, a lithium-containing metal oxide, a lithium-containing metal nitride, lithium phosphate (Li3PO4), or a lithium-containing transition metal oxide. Examples of lithium-containing metal oxides are Li2O-SiO2 or Li2O-SiO2-P2O5. Examples of lithium-containing metal nitrides are Li x P y O 1-z N z (0<z≦1) An example of the lithium-containing transition metal oxide is lithium titanium oxide.

[0195] The halide solid electrolyte is, for example, a solid electrolyte containing Li, at least one element selected from the group consisting of metal elements and metalloid elements other than Li, and a halogen element.

[0196] "Metalloid elements" are B, Si, Ge, As, Sb, and Te. "Metal 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).

[0197] It is desirable that the halide solid electrolyte be substantially free of sulfur. The term "substantially free of sulfur" means that the halide solid electrolyte 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 halide solid electrolyte as an impurity is, for example, 1 mol % or less. It is more desirable that the halide solid electrolyte be free of sulfur. A sulfur-free solid electrolyte is excellent in safety because it does not generate hydrogen sulfide even when exposed to the atmosphere.

[0198] The solid electrolyte layer 300 includes, for example, a halide solid electrolyte.

[0199] As a first example of the halogenated solid electrolyte, one containing Al is preferable because it provides relatively high ionic conductivity. One containing Li, Al, and X can also be used. X is at least one selected from the group consisting of F, Cl, Br, and I. For example, the halide solid electrolyte may contain LiAlX. X may be F. This results in a solid electrolyte layer 300 with high ionic conductivity of 1 μS / cm or more, as well as excellent atmospheric stability and heat resistance (e.g., heat resistance up to approximately 700°C to 800°C). A halogenated oxide (LiAl(X,O)), in which a portion of the halogen element X in LiAlX is replaced with oxygen, has a higher melting point and is harder than LiAlX. Therefore, by including such a solid electrolyte containing both halogenated oxide (LiAl(X,O)) and LiAlX as solid electrolyte A in the solid electrolyte layer 300, the effects of including solid electrolyte A can be obtained even in high-temperature regions. In addition to Li3AlX6, examples of halide solid electrolytes that are stable up to relatively high temperatures include Li2TiF6 (melting point: around 650°C to 700°C). A halide oxide (Li3Ti(X,O)6) in which part of the halogen element X in Li2TiF6 is substituted with oxygen may be further included together with Li2TiF6. This further densifies the solid electrolyte layer 300, achieving even higher ionic conductivity (e.g., 3 μS / cm or higher), while also achieving the effect of including solid electrolyte A (i.e., Li3Al(X,O)6-Li3Ti(X,O)6) containing halide oxide A and halide oxide B up to relatively high temperatures (e.g., approximately 650°C).

[0200] A second example of the halogenated solid electrolyte includes one containing Ti, and one containing Li, Ti, and X may be used. X is at least one selected from the group consisting of F, Cl, Br, and I. For example, the halide solid electrolyte may include Li2TiX6. X may be F. This results in a solid electrolyte layer 300 with high ionic conductivity of 1 μS / cm or more, as well as excellent atmospheric stability and heat resistance (e.g., heat resistance up to approximately 700°C to 800°C). A halogenated oxide (Li2Ti(X,O)6) in which a portion of the halogen element X in Li2TiX6 is replaced with oxygen has a higher melting point and is harder than Li2TiX6. Therefore, by including such a solid electrolyte containing a halogenated oxide (Li2Ti(X,O)6) coexisting with Li2TiX6 as solid electrolyte B in the solid electrolyte layer 300, the effects of including solid electrolyte B can be obtained up to high temperature ranges. An example of a halide solid electrolyte that is stable and hard up to relatively high temperatures is Li3AlF6 (melting point: around 800°C). A halide oxide (Li3Al(X,O)6) in which part of the halogen element X in Li3AlF6 is replaced with oxygen may be further included in the presence of Li2TiF6. This makes it easier for the solid electrolyte layer 300 to contain more pores and have a lower density, achieving even higher ionic conductivity (e.g., 3 μS / cm or higher), while also ensuring the effects of including solid electrolyte B containing halide oxide B and halide oxide A (i.e., Li2Ti(X,O)6-Li3Al(X,O)6) up to relatively high temperatures.

[0201] As described above, two or more materials (e.g., LiAlX-LiTiX) may be combined and used as the halide solid electrolyte in the solid electrolyte layer 300. As an example, the solid electrolyte layer 300 may include a halide solid electrolyte (LiAlF-LiTiF (LiAlF:LiTiF=70:30 (molar ratio))) and a halogenated oxide thereof.

[0202] The solid electrolyte layer 300 may contain, in addition to the solid electrolyte, a binder such as polyethylene oxide or polyvinylidene fluoride.

[0203] The thickness of the solid electrolyte layer 300 may be 5 μm or more and 500 μm or less, 10 μm or more and 500 μm or less, or 5 μm or more and 150 μm or less.

[0204] The solid electrolyte material may be composed of an agglomerate of particles, or may be composed of a sintered structure.

[0205] When the configuration of the battery 1000 according to this embodiment is compared with the configuration of the battery described in Patent Document 1, the following differences are found.

[0206] Patent Document 1 discloses a battery using a solid electrolyte containing Li, Ti, M, and X, which coats an active material. Here, M is at least one selected from the group consisting of metal elements and metalloid elements other than Li and Ti, and X is at least one selected from halogen elements. Patent Document 1 also describes that the solid electrolyte may contain oxygen. However, Patent Document 1 does not describe that the oxygen contained in the solid electrolyte is contained in the solid electrolyte layer or electrode layer as a halogenated oxide. For example, LiO is unstable in the atmosphere due to its tendency to react with moisture. Furthermore, AlO and TiO are insulating materials that do not have ionic conductivity and have significantly different thermal expansion properties from the halides contained in the solid electrolyte. Therefore, structural defects (e.g., peeling and cracks) are likely to occur at the interface between the Al oxide and Ti oxide and the halogenated oxide. Thus, it goes without saying that the properties of the battery change dramatically depending on how oxygen is contained in the coating layer. For this reason, the technology described in Patent Document 1 is different from the technology of the first embodiment of the present disclosure, which improves the reliability (e.g., mechanical strength and thermal shock resistance) of the solid electrolyte layer and / or the electrode layer.

[0207] Furthermore, Patent Document 1 neither discloses nor suggests that the mechanical strength and reliability of the battery can be improved by incorporating a halogenated oxide into the electrode layer and the solid electrolyte layer. In contrast, the battery 1000 according to the first embodiment includes a halogenated oxide, thereby improving the mechanical strength and reliability of the battery.

[0208] Second Embodiment A battery according to a second embodiment will be described below. The matters described in the first embodiment may be omitted as appropriate.

[0209] FIG. 2 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1100 according to the second embodiment.

[0210] Fig. 2(a) is a cross-sectional view of the battery 1100 of the second embodiment. Fig. 2(b) is a plan view of the battery 1100 of the second embodiment as viewed from below in the z-axis direction. Fig. 2(a) shows a cross-sectional view taken along dotted line II-II in Fig. 2(b).

[0211] As shown in FIG. 2, the battery 1100 according to the second embodiment differs from the battery 1000 according to the first embodiment in the configuration of the solid electrolyte layer.

[0212] The solid electrolyte layer 301 in the battery 1100 according to the second embodiment differs in that particles 400 of solid electrolyte A or solid electrolyte B are contained in the solid electrolyte layer 301 in a region on the side in contact with the first active material layer 120, for example, so as to be unevenly distributed in a layer, but are not contained in the region on the side in contact with the second active material layer 220. With this configuration, solid electrolyte A or solid electrolyte B can be selectively contained in an electrode layer where structural defects are likely to occur, for example, in a region on the electrode layer side containing an active material that expands and contracts greatly during charge and discharge or has a large thermal expansion coefficient. This allows the reliability of the battery 1100 to be efficiently improved.

[0213] A modified example of the battery 1100 according to the second embodiment may be a configuration in which the concentration of the particles 400 of solid electrolyte A or solid electrolyte B in a region of the solid electrolyte layer 301 that contacts the first active material layer 120 is higher than the concentration of the particles 400 of solid electrolyte A or solid electrolyte B in a region of the solid electrolyte layer 301 that contacts the second active material layer 220. This configuration can also efficiently improve the reliability of the battery 1100. In this specification, the concentration of the particles 400 of solid electrolyte A or solid electrolyte B refers to the concentration of the total amount of particles of solid electrolyte A and particles of solid electrolyte B.

[0214] Third Embodiment A battery according to a third embodiment will now be described. The matters described in the above embodiments may be omitted as appropriate.

[0215] FIG. 3 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1200 according to a third embodiment.

[0216] Fig. 3(a) is a cross-sectional view of the battery 1200 of the third embodiment. Fig. 3(b) is a plan view of the battery 1200 of the third embodiment as viewed from below in the z-axis direction. Fig. 3(a) shows a cross section taken along line III-III in Fig. 3(b).

[0217] As shown in FIG. 3, the battery 1200 according to the third embodiment differs from the battery 1000 according to the first embodiment in the configuration of the solid electrolyte layer.

[0218] The solid electrolyte layer 302 in the battery 1200 according to the third embodiment includes a first layer 302a in contact with the first electrode layer 100 and a second layer 302b in contact with the second electrode layer 200. The first layer 302a and the second layer 302b contain solid electrolytes having different compositions. The first layer 302a contains particles 400 of solid electrolyte A or solid electrolyte B. The second layer 302b contains neither solid electrolyte A nor solid electrolyte B. For example, from the standpoint of electrochemical stability, the solid electrolyte material in contact with the first electrode layer 100 and the solid electrolyte material in contact with the second electrode layer 200 may be made of different materials. As an example, a configuration may be used in which a halide solid electrolyte is used as the solid electrolyte material on the positive electrode layer side and a sulfide solid electrolyte is used as the solid electrolyte material on the negative electrode layer side. In such a case where the solid electrolyte layer is formed of two or more layers made of different materials, selectively incorporating solid electrolyte A or solid electrolyte B into the layer using a material that is prone to structural defects can selectively suppress defects, thereby efficiently improving the reliability of the battery 1200.

[0219] A modified example of the battery 1200 according to the third embodiment may be a configuration in which both the first layer 302a and the second layer 302b contain particles 400 of solid electrolyte A or solid electrolyte B, and the concentration of the particles 400 of solid electrolyte A or solid electrolyte B in the first layer 302a is higher than the concentration of the particles 400 of solid electrolyte A or solid electrolyte B in the second layer 302b. This configuration also efficiently improves the reliability of the battery 1200.

[0220] Fourth Embodiment A battery according to a fourth embodiment will now be described. The matters described in the above embodiments may be omitted as appropriate.

[0221] FIG. 4 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1300 according to a fourth embodiment.

[0222] Fig. 4(a) is a cross-sectional view of the battery 1300 of the fourth embodiment. Fig. 4(b) is a plan view of the battery 1300 of the fourth embodiment as viewed from below in the z-axis direction. Fig. 4(a) shows a cross section taken along line IV-IV in Fig. 4(b).

[0223] 4, the battery 1300 according to the fourth embodiment differs from the battery 1000 according to the first embodiment in that it further includes a side layer 500 containing solid electrolyte A or solid electrolyte B, which is arranged on at least one side surface selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the solid electrolyte layer 300. That is, the battery 1300 according to the fourth embodiment satisfies the above-mentioned configuration (II).

[0224] With this configuration, the battery 1300 according to the fourth embodiment can suppress external stress from the side surfaces and the occurrence of structural defects in the side surfaces, thereby achieving even higher reliability of the battery 1300.

[0225] In the battery 1300 according to the fourth embodiment, the lateral layer 500 includes a solid electrolyte A or a solid electrolyte B. The solid electrolyte A included in the lateral layer 500 is the same as the solid electrolyte A described in the first embodiment, and therefore a detailed description thereof will be omitted here. The solid electrolyte B included in the lateral layer 500 is the same as the solid electrolyte B described in the first embodiment, and therefore a detailed description thereof will be omitted here.

[0226] The side layer 500 may contain, for example, particles of the solid electrolyte A or the solid electrolyte B and an organic binder for binding. The side layer 500 can be formed, for example, by applying a paste containing particles of the solid electrolyte A or the solid electrolyte B and an organic binder onto at least one side surface selected from the group consisting of the first electrode layer 100, the second electrode layer 200, and the solid electrolyte layer 300, and drying the coating.

[0227] The thickness of the lateral layer 500 may be, for example, not less than 1 μm and not more than 30 μm.

[0228] The battery 1300 according to the fourth embodiment has a configuration in which the solid electrolyte A or the solid electrolyte B is also contained in the power generating element, i.e., it simultaneously satisfies the above configuration (I), but it does not necessarily have to satisfy the above configuration (I). In other words, it is not necessary for either the solid electrolyte A or the solid electrolyte B to be contained in the power generating element.

[0229] Fifth Embodiment A battery according to a fifth embodiment will now be described. Matters described in the above embodiments may be omitted as appropriate.

[0230] FIG. 5 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1400 according to a fifth embodiment.

[0231] Fig. 5(a) is a cross-sectional view of the battery 1400 of the fifth embodiment. Fig. 5(b) is a plan view of the battery 1400 of the fifth embodiment as viewed from below in the z-axis direction. Fig. 5(a) shows a cross section taken along the line V-V in Fig. 5(b).

[0232] As shown in FIG. 5 , the battery 1400 according to the fifth embodiment differs from the battery 1000 according to the first embodiment in that only the first electrode layer 100 contains particles 400 of solid electrolyte A or solid electrolyte B.

[0233] This configuration can suppress the problem of structural defects occurring in layers (e.g., electrode layers) that expand and contract significantly during charge / discharge cycles and thermal cycles, thereby improving the reliability of the battery 1400.

[0234] Sixth Embodiment A battery according to a sixth embodiment will now be described. The matters described in the above embodiments may be omitted as appropriate.

[0235] FIG. 6 is a cross-sectional view and a plan view showing a schematic configuration of a battery 1500 according to a sixth embodiment.

[0236] Fig. 6(a) is a cross-sectional view of a battery 1500 according to a sixth embodiment. Fig. 6(b) is a plan view of the battery 1500 according to the sixth embodiment, viewed from below in the z-axis direction. Fig. 6(a) shows a cross section taken along line VI-VI in Fig. 6(b).

[0237] As shown in FIG. 6 , the battery 1500 according to the sixth embodiment differs from the battery 1000 according to the first embodiment in that the concentrations of solid electrolyte A or solid electrolyte B contained in the first electrode layer 101 and the solid electrolyte layer 303 are different in each layer.

[0238] In the first electrode layer 101 and the solid electrolyte layer 303, the concentration of the particles 400 of solid electrolyte A or solid electrolyte B is higher on the outer periphery (side surface). In the battery 1500 shown in Fig. 6, the concentration of the particles 400 of solid electrolyte A or solid electrolyte B gradually changes continuously toward the outer periphery, but it may also be configured so that the concentration changes in a stepwise manner.

[0239] With this configuration, in the battery 1500, the outer periphery of the first electrode layer 101 (e.g., the first active material layer 121) and the solid electrolyte layer 303, which are prone to damage due to external impact (or peeling (interlayer or intralayer) due to charge / discharge or thermal cycles), can be surrounded by particles 400 of solid electrolyte A or solid electrolyte B with a high concentration. This effectively suppresses structural defects in the outer periphery of the power generating element, where structural defects are likely to occur. Note that the region with a high concentration of particles 400 of solid electrolyte A or solid electrolyte B may have a shape such as a rectangle, circle, polygon, etc. in plan view, and by surrounding the outer periphery and providing a shape that can protect the inside of the battery, high reliability can be achieved.

[0240] [Method for Manufacturing Battery] Next, an example of a method for manufacturing the battery according to this embodiment will be described. Hereinafter, a method for manufacturing the battery 1100 according to the second embodiment will be described.

[0241] In the following, an example will be described in which the first electrode layer 100 is a positive electrode layer and the second electrode layer 200 is a negative electrode layer. That is, in the following description, the first active material layer 120 is a positive electrode active material layer, the first current collector 110 is a positive electrode current collector, the second active material layer 220 is a negative electrode active material layer, and the second current collector 210 is a negative electrode current collector.

[0242] First, pastes to be used for printing the positive electrode active material layer and the negative electrode active material layer are prepared. As the solid electrolyte to be used for the mixture of the positive electrode active material layer and the negative electrode active material layer, for example, powder of a solid electrolyte (LiAlF-LiTiF) having an average particle size of about 3 μm and containing a halide as a main component is prepared. This powder has, for example, high ionic conductivity (for example, 1×10 -3 S / cm to 3 x 10 -3 S / cm) is used.

[0243] As the positive electrode active material, for example, a layered Li-Ni-Co-Al composite oxide (LiNi) having an average particle diameter of about 5 μm is used. 0.8 Co 0.15 Al 0.05 O2) powder is used.

[0244] When the solid electrolyte A is used, a halogenated oxide A and a halogenated oxide B are prepared as the solid electrolyte A, which are solid electrolyte materials Li3AlF6-Li2TiF6 with an average particle size of about 1 μm, in which part of the F ions is substituted with oxygen (for example, Li3AlF 5.8 O 0.1 , LiTiF 5.9 O 0.05 The synthesis of these halide oxides was carried out using the feed composition LiAlF 5.8 O 0.1 , and LiTiF 5.9 O 0.05 After preparing each of these, they are mixed in a predetermined ratio. 5.8 O 0.1 In this study, Li2CO3, Al2O3, and NH4F powders were mixed in a molar ratio of 3:1:17.4 in a mortar and pestle for about 10 minutes, and then heat-treated in nitrogen at 280°C for 1 hour to obtain halogenated oxide A, in which part of the F element was replaced with oxygen. 5.9 O 0.05 In the method described above, Li2CO3, TiO2, and NH4F powders are mixed uniformly in a molar ratio of 1:1:5.9, respectively, and then heat-treated in air at 270°C for 1 hour to obtain a halogenated oxide B in which part of the F element is substituted with oxygen. 5.8 O 0.1 and Li2TiF 5.9 O 0.05 and LiAlF are synthesized, and then mixed in a predetermined ratio (for example, in a molar ratio, 5.8 O 0.1 : Li2TiF 5.9 O 0.05 By uniformly mixing both materials at a ratio of 70:30, a halogenated oxide LiAlF 5.8 O0.1 -Li2TiF 5.9 O 0.05 The oxygen substitution amount of halides A and B can be controlled by reducing the amount of halogen (e.g., F) used to halogenate oxides or carbonates below the amount required for complete substitution (i.e., by reducing the amount of NH4F), resulting in the amount of oxygen remaining in the crystal lattice of the halide without being replaced by F. In this manner, the halogenated oxides were synthesized. The F source for the halogen element is not limited to NH4F. Any F-containing material that generates F gas upon thermal decomposition can be used. Therefore, halogen gas or a thermally decomposing Teflon®-based resin (e.g., PTFE) can also be used. Both halogenated oxide A and halogenated oxide B may be particulate, with particle diameters (measured by SEM observation) of approximately 1.2 μm for halogenated oxide A and approximately 0.9 μm for halogenated oxide B, for example. The halogenation of the oxides (substitution with halogen) proceeds as the halogen element gradually diffuses from the particle surface, which comes into contact with the halogen gas, to the interior during the heat treatment process. Therefore, after halogenating the oxide, the halogenated oxide particles tend to have a higher oxygen concentration inside the particle than at the surface. The remaining oxygen is likely to form long distances from the surface to the interior of the particle. Therefore, the high-oxygen-concentration regions within the particle are seamlessly formed, for example, within the halogen diffusion layer (i.e., deep within the particle), resulting in an integrated particle, which is structurally stable. Furthermore, the larger the particle size, the larger the high-oxygen-concentration regions tend to be inside the particle. This is because oxygen remains in regions far from the halogen diffusion. Furthermore, when the particle shape is scaly, needle-like, or elliptical, multiple high-oxygen-concentration regions may be formed. The oxygen substitution and content within the particle can be evaluated by, for example, composition analysis and observation of particle cross sections processed with an ion polisher using EPMA or EDS to determine the presence of high-oxygen-concentration regions within the halide A and B crystal particles and to assess the amount of oxygen. The particle size of halogenated oxides A and B can be controlled by adjusting the particle size of the halide or by further milling the halogenated oxide.

[0245] When solid electrolyte B is used, a halogenated oxide B and a halogenated oxide A are prepared as solid electrolyte B, which are solid electrolyte materials Li2TiF6-Li3AlF6 with an average particle size of about 1 μm, in which part of the F ions are substituted with oxygen (for example, Li2TiF 5.8 O 0.1 , LiAlF 5.9 O 0.05 The synthesis of these halide oxides is carried out with the starting composition Li2TiF 5.8 O 0.1 , and LiAlF 5.9 O 0.05 Specifically, the halogenated oxide B is Li2TiF 5.8 O 0.1 In the method, Li2CO3, TiO2, and NH4F powders are mixed uniformly in a molar ratio of 1:1:5.8, respectively, and then heat-treated in air at 280°C for 1 hour to obtain halogenated oxide B, in which part of the F element is substituted with oxygen. 5.8 O 0.1 powders of Li2CO3, Al2O3, and NH4F are mixed in a molar ratio of 3:1:17.7 in a mortar and pestle for about 10 minutes, and then heat-treated in nitrogen at 270°C for 1 hour to obtain a halide oxide A in which part of the F element is replaced with oxygen. 5.8 O 0.1 and Li3AlF 5.9 O 0.05 and LiTiF in a predetermined ratio (for example, in a molar ratio) 5.8 O 0.1 : LiAlF 5.9 O 0.05 By uniformly mixing both materials at a ratio of 30:70, a halogenated oxide Li2TiF 5.8 O 0.1 -LiAlF 5.9 O 0.05The amount of oxygen substitution in halides B and A can be controlled by reducing the amount of halogen (e.g., F) used to halogenate oxides or carbonates below the amount required for complete substitution (i.e., by reducing the amount of NH4F), resulting in the amount of oxygen remaining in the crystal lattice of the halide without being replaced by F. In this manner, the halogenated oxides were synthesized. The F source for the halogen element is not limited to NH4F. Any F-containing material that generates F gas upon thermal decomposition can be used. Therefore, halogen gas or a thermally decomposing Teflon®-based resin (e.g., PTFE) can also be used. Both halogenated oxide B and halogenated oxide A may be particulate, with particle diameters (measured by SEM observation) of approximately 1.2 μm for halogenated oxide B and approximately 0.9 μm for halogenated oxide A, for example. The halogenation of the oxides (substitution with halogen) proceeds as the halogen element gradually diffuses from the particle surface, which comes into contact with the halogen gas, to the interior during the heat treatment process. Therefore, after halogenating the oxide, the halogenated oxide particles tend to have a higher oxygen concentration inside the particle than at the surface. The remaining oxygen is likely to form long distances from the surface to the interior of the particle. Therefore, the high-oxygen-concentration regions within the particle are seamlessly formed, for example, within the halogen diffusion layer (i.e., deep within the particle), resulting in an integrated particle, which is structurally stable. Furthermore, the larger the particle size, the larger the high-oxygen-concentration regions tend to be inside the particle. This is because oxygen remains in regions far from the halogen diffusion. Furthermore, when the particle shape is scaly, needle-like, or elliptical, multiple high-oxygen-concentration regions may be formed. The oxygen substitution and content within the particle can be evaluated by, for example, composition analysis and observation of the particle cross-section processed with an ion polisher using EPMA or EDS to determine the presence of high-oxygen-concentration regions within the halide B and A crystal particles and the amount of oxygen. The particle size of the halogenated oxides B and A can be controlled by the particle size of the halide or by further pulverizing the halogenated oxide.

[0246] A paste for a positive electrode active material layer is prepared by dispersing a mixture containing the above-mentioned positive electrode active material, the above-mentioned solid electrolyte powder, and the above-mentioned halogenated oxide powder as solid electrolyte A or solid electrolyte B in an organic solvent or the like using a triple roll roller.

[0247] As the negative electrode active material, for example, powder of natural graphite having an average particle size of about 10 μm is used. A paste for a negative electrode active material layer is prepared in the same manner as the paste for a positive electrode active material layer, by dispersing a mixture containing the above-mentioned negative electrode active material and the above-mentioned solid electrolyte powder in an organic solvent or the like.

[0248] Next, copper foil with a thickness of, for example, approximately 30 μm is prepared as the material to be used as the positive electrode current collector and the negative electrode current collector. A paste for the positive electrode active material layer and a paste for the negative electrode active material layer are printed on one surface of each copper foil by screen printing, each in a predetermined shape and with a thickness of approximately 50 μm to 100 μm. The paste for the positive electrode active material layer and the paste for the negative electrode active material layer are dried at 80°C to 130°C to a thickness of 30 μm to 60 μm. The paste for the positive electrode active material layer contains the above-mentioned halogenated oxide powder, which is solid electrolyte A. This results in a current collector (copper foil) on which a positive electrode active material layer and a negative electrode active material layer are respectively formed.

[0249] Next, two types of solid electrolyte layer pastes are prepared, one containing the above-mentioned halogenated oxide powder of solid electrolyte A or solid electrolyte B dispersed in an organic solvent or the like, and the other not containing the halogenated oxide powder. The solid electrolyte layer paste containing the above-mentioned halogenated oxide powder of solid electrolyte A or solid electrolyte B is printed on the main surface of a positive electrode active material layer formed on a positive electrode current collector using a metal mask, to a thickness of, for example, about 80 μm to 120 μm. The solid electrolyte layer paste not containing the above-mentioned halogenated oxide powder of solid electrolyte A or solid electrolyte B is printed on the main surface of a negative electrode active material layer formed on a negative electrode current collector using a metal mask, to a thickness of, for example, about 80 μm to 120 μm. The positive electrode active material layer and the negative electrode active material layer, on whose main surfaces the solid electrolyte layer paste is printed, are then dried at 80° C. to 130° C. The thickness after drying is, for example, 50 μm to 70 μm.

[0250] Next, a solid electrolyte containing a halogenated oxide, which is solid electrolyte A or solid electrolyte B, printed on a positive electrode active material layer formed on a positive electrode current collector, and a solid electrolyte containing neither a halogenated oxide nor solid electrolyte A or solid electrolyte B, printed on a negative electrode active material layer formed on a negative electrode current collector, are laminated in contact with and facing each other, and the resulting laminate is placed in a die mold having a rectangular outer shape.

[0251] Next, a sheet having a thickness of, for example, about 70 μm and a modulus of elasticity of 5×10 6 An elastic sheet of about 100 Pa is inserted. With this configuration, pressure is applied to the laminate via the elastic sheet. Thereafter, pressure is applied for, for example, about 90 seconds while heating to 50°C. This results in a battery including a positive electrode layer, a negative electrode layer, and an electrolyte layer disposed between the positive electrode layer and the negative electrode layer.

[0252] The method for manufacturing a battery according to the present disclosure is not limited to the above-described example.

[0253] In the above-described manufacturing method, the paste for the positive electrode active material layer, the paste for the negative electrode active material layer, and the paste for the solid electrolyte layer are applied by printing, but the present invention is not limited to this. Examples of printing methods that may be used include a doctor blade method, a calendar method, a spin coating method, a dip coating method, an inkjet method, an offset method, a die coating method, and a spray method.

[0254] [Other Embodiments] (Additional Notes) The above description of the embodiments discloses the following techniques.

[0255] (Technology 1) A battery comprising: a first electrode layer; a second electrode layer; and a solid electrolyte layer disposed between the first electrode layer and the second electrode layer, wherein the battery satisfies at least one configuration selected from the group consisting of (I) and (II) below: (I) At least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer comprises a solid electrolyte containing a halogenated oxide. (II) The battery further comprises a side layer, the side layer comprising a solid electrolyte containing a halogenated oxide, disposed on a side surface of at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer. The halogenated oxide comprises at least one selected from the group consisting of a halogenated oxide A consisting of Li, M1, X1, and O, and a halogenated oxide B consisting of Li, M2, X2, and O; in the halogenated oxide A, M1 is at least one element selected from the group consisting of trivalent metal elements and trivalent metalloid elements, and X1 is at least one element selected from the group consisting of F, Cl, Br, and I; and in the halogenated oxide B, M2 is at least one element selected from the group consisting of tetravalent metal elements and tetravalent metalloid elements, and X2 is at least one element selected from the group consisting of F, Cl, Br, and I.

[0256] Halogenated oxides are generally harder than halides, and the above-mentioned halogenated oxide A in particular is harder than conventional halogenated solid electrolytes contained in batteries. When a solid electrolyte containing halogenated oxide A is included in the battery of Technology 1, the solid electrolyte containing halogenated oxide A acts as a reinforcing material or an anchor material between particles (e.g., between solid electrolyte particles, between active material particles, or between solid electrolyte particles and active material particles). Therefore, according to the battery of Technology 1, the inclusion of halogenated oxide A improves external impact resistance and strength. The desired impact resistance and strength can be adjusted by the type of halogen element constituting halogenated oxide A and the oxygen content in halogenated oxide A, thereby achieving high battery reliability. In this way, the battery of Technology 1 can improve reliability. Hereinafter, a solid electrolyte containing halogenated oxide A may also be referred to as "solid electrolyte A."

[0257] In addition, a combination of multiple halogen elements may be used in the halogenated oxide A. This allows a battery with desired performance depending on the application. For example, when the halogenated oxide A contains an F element, the battery of Technology 1 can have excellent atmospheric stability.

[0258] Here, the halogenated oxide A can be regarded as a substance obtained by substituting a part of the halogen element in a halide with oxygen, for example. In this case, the oxygen content in the halogenated oxide A can be regarded as the oxygen substitution amount in the halogenated oxide A, for example.

[0259] Halogenated oxides are generally harder than halides, and the above-mentioned halogenated oxide B in particular is harder than conventional halogenated solid electrolytes contained in batteries. When a solid electrolyte containing halogenated oxide B is included in a battery of Technology 1, the solid electrolyte containing halogenated oxide B suppresses densification of components containing the solid electrolyte (e.g., solid electrolyte layer, electrode layer, etc.), increasing the number of pores and lowering the density. This reduces the heat capacity of components such as the solid electrolyte layer and electrode layer, thereby reducing cracks caused by thermal shock and thermal cycling. This results in a battery with excellent durability against external stress and resistance to thermal shock. The type of halogen element constituting halogenated oxide B and the oxygen content in halogenated oxide B can be adjusted to the desired impact resistance and thermal shock resistance, thereby achieving high battery reliability. In this way, the battery of Technology 1 can improve reliability. Hereinafter, a solid electrolyte containing halogenated oxide B may also be referred to as "solid electrolyte B."

[0260] It should be noted that a combination of multiple halogen elements may be used in the halogenated oxide B. This allows a battery with desired performance depending on the application. For example, when the halogenated oxide B contains an F element, the battery of Technology 1 can have excellent atmospheric stability and high ionic conductivity of, for example, 1 μS / cm or more.

[0261] Here, the halogenated oxide B can be regarded as a substance obtained by substituting a part of the halogen elements in a halide with oxygen, for example. In this case, the oxygen content in the halogenated oxide B can be regarded as the oxygen substitution amount in the halogenated oxide B, for example.

[0262] The above effects can be achieved with either the configuration (I) or (II). For example, when the configuration (I) is satisfied, the strength of the electrode layer and / or electrolyte layer, which are the power-generating elements of the battery, can be improved, thereby improving the reliability of the battery. Furthermore, when the configuration (II) is satisfied, structural defects (i.e., cracks or peeling originating from the side surfaces) that tend to be caused by external impacts and thermal impacts can be effectively suppressed by the side surface layer containing solid electrolyte A or solid electrolyte B, thereby improving the reliability of the battery.

[0263] (Technology 2) The battery according to Technology 1, wherein the solid electrolyte further contains a halide.

[0264] Halides share a common structure with halide oxides in that they both contain a halogen element. Therefore, halides have a thermal expansion coefficient similar to that of halide oxides, good bondability, and good affinity with halide oxides. By including solid electrolyte A or solid electrolyte B that further contains a halide, the battery of Technology 2 can suppress the occurrence of structural defects (e.g., interfacial peeling and cracking between the solid electrolyte and halide oxide) during charge / discharge cycles and thermal shock, thereby achieving high reliability.

[0265] (Technology 3) The battery according to Technology 1 or 2, wherein the halogenated oxide includes the halogenated oxide A.

[0266] With the above-described configuration, the battery of Technique 3 includes a solid electrolyte containing halogenated oxide A, i.e., solid electrolyte A. Therefore, as described above, reliability can be improved.

[0267] (Technology 4) The battery according to Technology 3, wherein the halogenated oxide further contains the halogenated oxide B, and the ratio of the amount of substance of O to the total amount of substance of X1 and O (O / (X1+O)) in the halogenated oxide A is equal to or greater than the ratio of the amount of substance of O to the total amount of substance of X2 and O (O / (X2+O)) in the halogenated oxide B.

[0268] This configuration results in a more reliable battery. For example, a wider range of characteristic control is possible by adjusting the content ratio of halogenated oxide A to halogenated oxide B, and the type of halogen element and oxygen content of halogenated oxide A and halogenated oxide B. This allows for broader control to improve battery characteristics and reliability. The ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)), specified in the battery of Technology 4, can be considered the oxygen content in halogenated oxide A. Furthermore, the ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)) can be considered the oxygen content in halogenated oxide B.

[0269] For example, halide oxide A tends to have a higher melting point and be harder than halide oxide B. By making the oxygen content of halide oxide A equal to or greater than that of halide oxide B, the solid electrolyte A's function as a reinforcing material and an anchor material between particles becomes more effective. Furthermore, by including halide oxide B, which is softer than halide oxide A, the solid electrolyte A not only ensures interparticle adhesion but also absorbs expansion and contraction during charge / discharge and thermal cycles. This results in densification of the battery components and suppression of structural defects. As a result, the battery of Technology 4 has excellent mechanical strength and higher reliability.

[0270] (Technology 5) The battery according to Technology 3 or 4, wherein the solid electrolyte further contains a halide A, and the halide A consists of Li, the M1, and the X1.

[0271] Halide A has a thermal expansion coefficient close to that of halide oxide A, has good bonding properties, and has good affinity with halide oxide A. This allows for the production of a solid electrolyte A having high, excellent ionic conductivity, for example, of 1 μS / cm or more. As a result, a highly reliable and excellent-performance battery can be obtained.

[0272] (Technology 6) The battery according to Technology 4, wherein the solid electrolyte further contains a halide B, and the halide B consists of Li, the M2, and the X2.

[0273] Halide B has a thermal expansion coefficient close to that of halide oxide B, has good bonding properties, and has good affinity with halide oxide B. This allows for the production of a solid electrolyte A having high, excellent ionic conductivity, for example, of 1 μS / cm or more. As a result, a highly reliable and excellent-performance battery can be obtained.

[0274] (Technology 7) The battery according to Technology 1 or 2, wherein the halogenated oxide includes the halogenated oxide B.

[0275] With the above-described configuration, the battery of Technique 7 includes a solid electrolyte containing halogenated oxide B, i.e., solid electrolyte B. Therefore, as described above, reliability can be improved.

[0276] (Technology 8) The battery according to Technology 7, wherein the halogenated oxide further includes the halogenated oxide A, and the ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)) in the halogenated oxide B is greater than the ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)) in the halogenated oxide A.

[0277] This configuration results in a more reliable battery. For example, a wider range of characteristic control is possible by adjusting the content ratio of halogenated oxide B to halogenated oxide A, the type of halogen element constituting each halogenated oxide, and the oxygen content ratio for halogenated oxide B and halogenated oxide A. This allows for broader control to improve battery characteristics and reliability. The ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)), specified in the battery of Technology 2, can be considered the oxygen content ratio in halogenated oxide B. Furthermore, the ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)) can be considered the oxygen content ratio in halogenated oxide A.

[0278] For example, halide oxide B tends to have a lower melting point and be softer than halide oxide A. By increasing the oxygen content in halide oxide B relative to that in halide oxide A to harden halide oxide B, the solid electrolyte B's improved impact resistance and thermal shock resistance are more readily achieved. Furthermore, by including halide oxide A, which is harder than halide oxide B, solid electrolyte B can be a composite material containing materials of different hardness, thereby dispersing the fracture limits of flexural strength and toughness. This allows solid electrolyte B to produce a dense battery with excellent mechanical strength. Furthermore, since solid electrolyte B contains multiple materials with different compression characteristics, the deformation pressure is dispersed. Therefore, air is gradually expelled from the powder compact during the compression process, reducing the amount of residual air trapped inside the powder compact and suppressing springback (i.e., expansion of the powder compact after pressure release). This alleviates the problem of cracks and fractures in the powder compact, thereby further improving the reliability of the battery.

[0279] (Technology 9) The battery according to Technology 7 or 8, wherein the solid electrolyte further contains a halide B, and the halide B consists of Li, the M2, and the X2.

[0280] Halide B has a thermal expansion coefficient close to that of halide oxide B, has good bonding properties, and has good affinity with halide oxide B. This makes it possible to obtain a solid electrolyte B having high, excellent ionic conductivity of, for example, 1 μS / cm or more and improved atmospheric stability. As a result, a highly reliable and excellent-performance battery can be obtained.

[0281] (Technology 10) The battery according to Technology 8, wherein the solid electrolyte further contains a halide A, and the halide A consists of Li, the M1, and the X1.

[0282] Halide A has a thermal expansion coefficient close to that of halide oxide A, has good bonding properties, and has good affinity with halide oxide A. This makes it possible to obtain a solid electrolyte B having high, excellent ionic conductivity of, for example, 1 μS / cm or more and improved atmospheric stability. As a result, a highly reliable and excellent-performance battery can be obtained.

[0283] (Technology 11) The battery according to any one of Techniques 1 to 10, wherein the solid electrolyte is in a particulate form.

[0284] This allows the solid electrolyte containing a halogenated oxide to be incorporated into the first electrode layer, the second electrode layer, and the solid electrolyte layer together with other solid electrolytes. Therefore, the desired components can be provided with improved impact resistance and strength at the microstructure level (e.g., particle level). This allows for a highly reliable battery. Furthermore, this configuration allows the battery of the present disclosure to be applied to all-solid-state batteries formed from a compact, such as those formed using sulfide-based solid electrolytes and halide-based solid electrolytes, which have excellent ionic conductivity. This allows for a highly reliable all-solid-state battery with excellent performance.

[0285] (Technology 12) The battery according to Technology 11, wherein the particles of the solid electrolyte contain the halogenated oxide and a halide.

[0286] The solid electrolyte particles contain a halide and a hard halide oxide, which improves the bonding between the particles. Therefore, the desired components can be provided with improved impact resistance and strength at the microstructure level (e.g., particle level). In particular, the effects of improved bonding between particles and strength are achieved in the compact. This configuration results in a battery with excellent reliability, particularly in terms of impact resistance and flexural strength.

[0287] (Technology 13) The battery according to Technology 11 or 12, wherein the solid electrolyte particles contain the halogenated oxide.

[0288] This allows the hard halide oxide to be located inside the particles, while a softer material, such as a halide, is located on the particle surface, enhancing the interparticle adhesion while providing the hard core as a reinforcing material. This provides high interparticle bonding and improved strength, particularly in compacts. This results in batteries with high reliability, for example, in terms of impact resistance and flexural strength.

[0289] (Technology 14) The battery according to any one of Techniques 11 to 13, wherein the volume ratio of the halide oxide to the solid electrolyte particles increases as the volume of the particles increases.

[0290] This allows the softness (e.g., deformability) or hardness of the particles of the solid electrolyte containing the halide oxide to be adjusted over a wide range, for example, by changing the particle size. Furthermore, the voids between the hard, large particles with a larger volume fraction of the halide oxide are filled with soft, small particles with a smaller volume fraction of the halide oxide, further improving the bonding between the particles. Therefore, the bonding between the particles and the strength are improved, particularly in the powder compact.

[0291] (Technology 15) The battery according to any one of technologies 11 to 14, wherein the particles of the solid electrolyte have a plurality of regions in which the halide oxide is present.

[0292] This allows the softness (e.g., deformability) or hardness of the solid electrolyte particles containing halogenated oxide to be adjusted over a wider range. This improves the reliability of the battery against external stress and thermal cycles. The softness or hardness of the solid electrolyte particles containing halogenated oxide can be adjusted by adjusting the size and number of regions where halogenated oxides are present. Such particles having multiple regions where halogenated oxides are present within the particles can be formed, for example, by mixing a halogenated oxide powder obtained by halogenating an oxide with a halide solid electrolyte by a mechanochemical method to form composite particles. Furthermore, particles having multiple regions where halogenated oxides are present within the particles can also be formed by oxidizing a halide having a scale-like or needle-like shape.

[0293] (Technology 16) The battery according to any one of Techniques 1 to 15, wherein M1 contains Al.

[0294] As a result, the solid electrolyte containing the halogenated oxide A can have high ionic conductivity, for example, 1 μS / cm or more, and high heat resistance due to having a melting point, for example, 750° C. or more. Therefore, a battery with even better performance and heat resistance can be obtained. In addition, in this case, by increasing the oxygen content in the halogenated oxide A, the heat resistance and hardness of the solid electrolyte containing the halogenated oxide can be further improved, thereby further improving the reliability of the battery.

[0295] (Technology 17) The battery according to any one of technologies 1 to 16, wherein M2 contains Ti.

[0296] As a result, the solid electrolyte containing halogenated oxide B can have high ionic conductivity, for example, 1 μS / cm or more, and high heat resistance due to its melting point, for example, 700° C. or more. Therefore, a battery with even better performance and heat resistance can be obtained. In addition, in this case, by increasing the oxygen content in halogenated oxide B, the heat resistance and hardness of the solid electrolyte containing halogenated oxide B can be further improved, thereby further improving the reliability of the battery.

[0297] (Technology 18) The battery according to any one of technologies 1 to 17, wherein X1 contains F.

[0298] By including F in the halogenated oxide A, the solid electrolyte containing the halogenated oxide A can have high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 600° C. or more. Therefore, a more reliable battery can be obtained. Here, excellent atmospheric stability means, for example, excellent durability against normal atmospheric moisture.

[0299] (Technology 19) The battery according to any one of technologies 1 to 18, wherein X2 contains F.

[0300] By including F in the halogenated oxide B, the solid electrolyte containing the halogenated oxide B can have high ionic conductivity, for example, 1 μS / cm or more, and can have excellent atmospheric stability and high-temperature stability, for example, at 600° C. or more. Therefore, a more reliable battery can be obtained. Here, excellent atmospheric stability means, for example, excellent durability against normal atmospheric moisture.

[0301] (Technology 20) The battery according to any one of technologies 1 to 19, wherein the halogenated oxide contains at least one selected from the group consisting of Na, K, Ca, Si, Zr, Ga, P, and Nb.

[0302] The above elements act as auxiliary agents to promote the solid-phase reaction during the synthesis of halogenated oxides, thereby lowering the solid-phase reaction temperature of halogenated oxides and homogenizing the reaction state. This reduces deviations from the desired composition and compositional variations due to evaporation of constituent components. This results in a solid electrolyte with excellent properties. Furthermore, the inclusion of these elements prevents halogenated oxides from sintering too hard, making them easier to pulverize and enabling fine pulverization (e.g., into particles with a particle size of 1 μm or less). This increases the surface area of ​​the halogenated oxides, further enhancing the benefits of solid electrolytes containing halogenated oxides (e.g., as reinforcing materials and anchor materials between particles). Furthermore, finely divided halogenated oxides can be used in batteries that require thinner layers.

[0303] (Technology 21) The battery according to any one of Techniques 1 to 20, wherein the battery satisfies (I), the first electrode layer includes active material particles and a coating layer that coats at least a portion of a surface of the active material particles, and the coating layer includes the solid electrolyte.

[0304] This strengthens the interfacial adhesion between the active material and the solid electrolyte contained in the electrode due to the effect of the solid electrolyte containing the halide oxide as an anchor material, thereby reducing the interfacial resistance. This allows for the production of a battery with excellent performance (e.g., charge / discharge characteristics, durability, etc.). Here, battery durability refers to, for example, the cycle characteristics and high-temperature stability of the battery.

[0305] (Technology 22) The battery according to Technology 21, wherein the first electrode layer is a positive electrode layer.

[0306] This reduces the interface resistance between the positive electrode active material and the solid electrolyte contained in the electrode. Furthermore, Joule heat generated by the positive electrode, which is prone to heat generation, is reduced by reducing the resistance, resulting in high heat resistance. This allows for a battery with excellent performance (e.g., charge / discharge characteristics and durability). Here, battery durability refers to, for example, the cycle characteristics and high-temperature stability of the battery.

[0307] (Technology 23) The battery according to any one of Techniques 3 to 6, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (1): Li3AlX36 ... formula (1) In the composition formula (1), X3 is at least one selected from the group consisting of F, Cl, Br, and I.

[0308] This provides the solid electrolyte A with high ionic conductivity, for example, 1 μS / cm or more, and high reliability, thereby making it possible to obtain a battery with even higher reliability.

[0309] (Technology 24) The battery according to Technology 23, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (2): Li3AlF6 Formula (2).

[0310] This allows the solid electrolyte A to have further atmospheric stability. Therefore, fluctuations in the properties of the solid electrolyte A during the manufacturing process can be suppressed, allowing desired properties to be reproducibly obtained. Furthermore, strict dew point environmental control (i.e., temperature and humidity control) during the manufacturing process is no longer necessary, thereby reducing the manufacturing cost of the battery.

[0311] (Technology 25) The battery according to any one of Technologies 7 to 10, wherein the solid electrolyte includes a crystalline phase represented by the following composition formula (3): Li2TiX46 ... formula (3) In the composition formula (3), X4 is at least one selected from the group consisting of F, Cl, Br, and I.

[0312] This provides the solid electrolyte B with high ionic conductivity, for example, 1 μS / cm or more, and high reliability, thereby making it possible to obtain a battery with even higher reliability.

[0313] (Technology 26) The battery according to Technology 25, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (4): Li2TiF6 Formula (4).

[0314] This allows the solid electrolyte B to have further atmospheric stability. Therefore, fluctuations in the properties of the solid electrolyte B during the manufacturing process can be suppressed, allowing desired properties to be reproducibly obtained. Furthermore, strict dew point environmental control (i.e., temperature and humidity control) during the manufacturing process is no longer necessary, thereby reducing the manufacturing cost of the battery.

[0315] (Technology 27) The battery according to any one of Techniques 1 to 26, wherein the halogenated oxide A includes an amorphous portion A.

[0316] This can impart softness to the halogenated oxide A, thereby improving the densification and interparticle adhesion of the solid electrolyte containing the halogenated oxide A. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (e.g., thermal stress), resulting in a battery with excellent performance and reliability.

[0317] (Technology 28) The amorphous portion A has a composition represented by the following composition formula (5): Li3M1(X1 1-a O a / 2 )6 Formula (5) In the composition formula (5), the a satisfies 0<a<1.

[0318] Therefore, the halogenated oxide A can be regarded as a composite material containing a soft material and a hard material. Therefore, the mechanical strength can be further improved by the effect of the halogenated oxide A while improving densification and interparticle binding. Therefore, a battery with higher reliability can be obtained.

[0319] (Technology 29) The battery according to Technology 28, wherein in the amorphous portion A, M1 contains Al.

[0320] As a result, the solid electrolyte containing the halogenated oxide A can have atmospheric stability, high-temperature durability up to about 800°C, and high ionic conductivity of, for example, 1 μS / cm or more, thereby providing a battery with higher reliability.

[0321] (Technology 30) The battery according to any one of Techniques 1 to 29, wherein the halogenated oxide B includes an amorphous portion B.

[0322] This can impart softness to the halogenated oxide B, thereby improving the densification and interparticle adhesion of the solid electrolyte containing the halogenated oxide B. This improves the ionic conductivity, mechanical strength, and thermal shock resistance (for example, thermal stress), resulting in a battery with excellent performance and reliability.

[0323] (Technology 31) The amorphous portion B has a composition represented by the following composition formula (6): Li2M2(X2 1-b O b / 2 ) 6 Formula (6) In the composition formula (6), the b satisfies 0<b<1.

[0324] Therefore, the halide oxide B can be regarded as a composite material containing a soft material and a hard material. Therefore, the mechanical strength can be further improved by the effect of the halide oxide B while improving densification and interparticle binding, thereby resulting in a battery with higher reliability.

[0325] (Technology 32) The battery according to Technology 31, wherein in the amorphous portion B, M2 contains Ti.

[0326] As a result, the solid electrolyte containing the halogenated oxide B can have atmospheric stability, high-temperature durability up to about 700°C, and high ionic conductivity of, for example, 1 μS / cm or more, thereby providing a battery with higher reliability.

[0327] (Technology 33) The battery according to any one of technologies 1 to 32, wherein the halogenated oxide A further contains at least one selected from the group consisting of Na, Ca, Si, Zr, and Ga.

[0328] The above elements act as auxiliary agents that promote the solid-phase reaction when synthesizing the halogenated oxide A, thereby lowering the solid-phase reaction temperature of the halogenated oxide A and homogenizing the reaction state. This reduces deviation from the desired composition of the halogenated oxide A due to evaporation of the constituent components, as well as compositional variation. This results in a solid electrolyte with excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength.

[0329] (Technology 34) The battery according to any one of technologies 1 to 33, wherein the halogenated oxide B further contains at least one selected from the group consisting of Na, K, P, Si, Zr, and Nb.

[0330] The above elements act as auxiliary agents that promote the solid-phase reaction when synthesizing the halide oxide B, thereby lowering the solid-phase reaction temperature of the halide oxide B and homogenizing the reaction state. This reduces deviation from the desired composition of the halide oxide B due to evaporation of the constituent components, as well as compositional variation. This results in a solid electrolyte with excellent properties, such as high ionic conductivity of 1 μS / cm or more and further improved mechanical strength.

[0331] (Technology 35) The battery according to any one of technologies 1 to 34, wherein the halogenated oxide B has a melting point lower than that of the halogenated oxide A.

[0332] When halide oxide B has a lower melting point than halide oxide A, halide oxide B is usually softer than halide oxide A. Therefore, for example, when a solid electrolyte containing a halide oxide is included in an electrode layer, halide oxide B tends to deform and fill voids in the solid electrolyte layer and / or electrode layer formed by a mixture containing halide oxide A or another solid electrolyte. Filling of such voids with halide oxide B occurs, for example, when stacking and pressurizing layers during battery production. Therefore, the solid electrolyte layer and / or electrode layer containing a solid electrolyte containing a halide oxide tends to become densified. Note that, in commonly used hot pressing, the halide oxide B in particular becomes more deformable. Such densification improves, for example, the ionic conductivity of the solid electrolyte layer and / or electrode layer and suppresses the occurrence of structural defects (e.g., voids and cracks). Therefore, fine voids and cracks, which are the starting points for characteristic degradation due to external stress and thermal cycling, are reduced, resulting in a highly reliable solid electrolyte layer and / or electrode layer. Therefore, a battery with good performance and excellent reliability can be realized.

[0333] (Technology 36) The battery according to any one of Techniques 1 to 35, wherein the halogenated oxide B is softer than the halogenated oxide A.

[0334] For example, when a solid electrolyte containing a halogenated oxide is included in an electrode layer, halogenated oxide B, which is softer than halogenated oxide A, tends to deform and fill voids in the solid electrolyte layer and / or electrode layer formed by a mixture containing halogenated oxide A or another solid electrolyte. The filling of such voids with halogenated oxide B occurs, for example, when stacking and pressurizing layers during battery production. Therefore, the solid electrolyte layer and / or electrode layer containing the halogenated oxide-containing solid electrolyte tends to become densified. This densification improves the ionic conductivity of the solid electrolyte layer and / or electrode layer and suppresses the occurrence of structural defects (e.g., voids and cracks). Furthermore, the soft halogenated oxide B reduces springback after pressure release, thereby suppressing the occurrence of structural defects (e.g., cracks and cracks) that occur when pressure is released. This reduces fine voids and cracks, which are the starting points for characteristic degradation due to external stress and thermal cycling, resulting in a highly reliable solid electrolyte layer and / or electrode layer. This allows for the realization of a battery with excellent performance and reliability. The comparison of the softness between the halogenated oxide B and the halogenated oxide A can be evaluated by a method such as micro-Vickers.

[0335] (Technology 37) The battery according to any one of Techniques 3 to 6, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (7): Li2M2F6 Formula (7).

[0336] As a result, for example, when the halogenated oxide A contains a crystalline phase represented by the above composition formula (1): Li3AlX36, a solid electrolyte A softer than the halogenated oxide A can be obtained.

[0337] (Technology 38) The battery according to Technology 37, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (8): Li2TiF6 Formula (8).

[0338] This allows for the production of a solid electrolyte A having ionic conductivity (e.g., ionic conductivity exceeding 1 μS / cm) comparable to that of the halogenated oxide A containing the crystalline phase represented by the composition formula (1): LiAlX36. This also allows for the production of a solid electrolyte A that is stable in the atmosphere. This allows for the production of a solid electrolyte A that has high ionic conductivity and high reliability. This allows for the production of a battery with excellent performance and reliability.

[0339] (Technology 39) The battery according to any one of Techniques 7 to 10, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (9): Li3M1F6 Formula (9).

[0340] As a result, for example, when the halide oxide B contains a crystalline phase represented by the above composition formula (3): Li2TiX46, a solid electrolyte B harder than the halide oxide B can be obtained.

[0341] (Technology 40) The battery according to Technology 39, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (10): Li3AlF6 Formula (10).

[0342] This allows for the production of a solid electrolyte B having ionic conductivity (e.g., ionic conductivity exceeding 1 μS / cm) equal to or greater than that of the halide oxide B containing the crystalline phase represented by the composition formula (3): LiTiX46. This also allows for the production of a solid electrolyte B that is stable in the atmosphere and at high temperatures. This allows for the production of a solid electrolyte B that has high ionic conductivity and high reliability. This allows for the production of a battery with excellent performance and reliability.

[0343] While the battery according to the present disclosure has been described above based on the embodiments, the present disclosure is not limited to these embodiments. As long as they do not deviate from the gist of the present disclosure, various modifications conceivable by those skilled in the art to the embodiments and other forms constructed by combining some of the components of the embodiments are also included in the scope of the present disclosure.

[0344] Furthermore, the above-described embodiments can be modified, replaced, added, omitted, and the like in various ways within the scope of the claims or their equivalents.

[0345] The battery according to the present disclosure can be used as a secondary battery such as an all-solid-state lithium battery used in various electronic devices or automobiles, for example.

Claims

1. A battery comprising: a first electrode layer; a second electrode layer; and a solid electrolyte layer disposed between the first electrode layer and the second electrode layer, wherein the battery satisfies at least one of the following conditions (I) and (II): (I) at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer comprises a solid electrolyte containing a halogenated oxide. (II) The battery further comprises a side layer, the side layer comprising a solid electrolyte containing a halogenated oxide, disposed on a side surface of at least one selected from the group consisting of the first electrode layer, the second electrode layer, and the solid electrolyte layer. The halogenated oxide comprises at least one selected from the group consisting of a halogenated oxide A consisting of Li, M1, X1, and O, and a halogenated oxide B consisting of Li, M2, X2, and O; in the halogenated oxide A, M1 is at least one element selected from the group consisting of trivalent metal elements and trivalent metalloid elements, and X1 is at least one element selected from the group consisting of F, Cl, Br, and I; and in the halogenated oxide B, M2 is at least one element selected from the group consisting of tetravalent metal elements and tetravalent metalloid elements, and X2 is at least one element selected from the group consisting of F, Cl, Br, and I.

2. The battery according to claim 1, wherein the solid electrolyte further contains a halide.

3. The battery according to claim 1, wherein the halogenated oxide comprises the halogenated oxide A.

4. The battery according to claim 3, wherein the halogenated oxide further contains the halogenated oxide B, and the ratio of the amount of substance of O to the sum of the amounts of substances of X1 and O in the halogenated oxide A (O / (X1+O)) is equal to or greater than the ratio of the amount of substance of O to the sum of the amounts of substances of X2 and O in the halogenated oxide B (O / (X2+O)).

5. The battery according to claim 3, wherein the solid electrolyte further contains a halide A, and the halide A consists of Li, the M1, and the X1.

6. The battery according to claim 4, wherein the solid electrolyte further contains a halide B, and the halide B consists of Li, the M2, and the X2.

7. The battery according to claim 1, wherein the halogenated oxide comprises the halogenated oxide B.

8. The battery according to claim 7, wherein the halogenated oxide further comprises the halogenated oxide A, and the ratio of the amount of substance of O to the sum of the amounts of substance of X2 and O (O / (X2+O)) in the halogenated oxide B is greater than the ratio of the amount of substance of O to the sum of the amounts of substance of X1 and O (O / (X1+O)) in the halogenated oxide A.

9. The battery according to claim 7, wherein the solid electrolyte further contains a halide B, and the halide B consists of Li, the M2, and the X2.

10. The battery according to claim 8, wherein the solid electrolyte further contains a halide A, and the halide A consists of Li, the M1, and the X1.

11. The battery of claim 1, wherein the solid electrolyte is in particulate form.

12. The battery according to claim 11, wherein the particles of the solid electrolyte include the halogenated oxide and a halide.

13. The battery according to claim 11, wherein the solid electrolyte particles contain the halide oxide.

14. The battery according to claim 11, wherein the volume ratio of the halide oxide to the solid electrolyte particles increases as the volume of the particles increases.

15. The battery of claim 11, wherein the particles of the solid electrolyte comprise a plurality of regions in which the halide oxide is present.

16. The battery of claim 1, wherein M1 comprises Al.

17. The battery of claim 1, wherein M2 comprises Ti.

18. The battery of claim 1, wherein X1 includes F.

19. The battery of claim 1, wherein X2 includes F.

20. The battery according to claim 1, wherein the halide oxide contains at least one selected from the group consisting of Na, K, Ca, Si, Zr, Ga, P, and Nb.

21. The battery according to claim 1, wherein the battery satisfies (I), the first electrode layer includes active material particles and a coating layer that covers at least a portion of the surface of the active material particles, and the coating layer includes the solid electrolyte.

22. The battery of claim 21, wherein the first electrode layer is a positive electrode layer.

23. The battery according to claim 3, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (1): Li3AlX36 ... formula (1) In the composition formula (1), X3 is at least one selected from the group consisting of F, Cl, Br, and I.

24. The battery according to claim 23, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (2): Li3AlF6 ... formula (2).

25. The battery according to claim 7, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (3): Li2TiX46 ... Formula (3) In the composition formula (3), X4 is at least one selected from the group consisting of F, Cl, Br, and I.

26. The battery according to claim 25, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (4): Li2TiF6 ... formula (4).

27. The battery according to claim 1, wherein the halogenated oxide A includes an amorphous portion A.

28. The amorphous portion A has a composition represented by the following composition formula (5): Li3M1(X1 1-a O a / 2 )6 Formula (5) The battery according to claim 27, wherein in the composition formula (5), the a satisfies 0<a<1.

29. The battery according to claim 28, wherein in the amorphous portion A, M1 contains Al.

30. The battery according to claim 1, wherein the halogenated oxide B includes an amorphous portion B.

31. The amorphous portion B has a composition represented by the following composition formula (6): Li2M2(X2 1-b O b / 2 )6 Formula (6) The battery according to claim 30, wherein in the composition formula (6), the b satisfies 0<b<1.

32. The battery according to claim 31, wherein in the amorphous portion B, M2 contains Ti.

33. The battery according to claim 1, wherein the halide oxide A further contains at least one selected from the group consisting of Na, Ca, Si, Zr, and Ga.

34. The battery according to claim 1, wherein the halide oxide B further contains at least one selected from the group consisting of Na, K, P, Si, Zr, and Nb.

35. The battery of claim 1, wherein the halogenated oxide B has a lower melting point than the halogenated oxide A.

36. The battery of claim 1, wherein the halogenated oxide B is softer than the halogenated oxide A.

37. The battery according to claim 3, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (7): Li2M2F6 ... formula (7).

38. The battery according to claim 37, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (8): Li2TiF6 ... formula (8).

39. The battery according to claim 7, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (9): Li3M1F6 ... formula (9).

40. The battery according to claim 39, wherein the solid electrolyte contains a crystalline phase represented by the following composition formula (10): Li3AlF6 ... formula (10).

Images