Solid electrolyte for solid-state battery, solid-state battery, and battery package

Abstract

Provided is a solid-state battery electrolyte for use in solid-state batteries that has better performance. This solid-state electrolyte for use in solid-state batteries has a first solid-state electrolyte of a perovskite structure having a lattice constant that is a 3.8-4.1 Å integer multiple, and a second solid-state electrolyte of a reverse perovskite structure having a lattice constant that is a 3.8-4.1 Å integer multiple.

Description

[Technical Field]

[0001] The present disclosure relates to a solid electrolyte for a solid-state battery, and a solid-state battery and battery package including the same. [Background technology]

[0002] Due to the widespread use of various electronic devices such as mobile phones, secondary batteries have been developed as power sources that are small, lightweight, and capable of achieving high energy density. These secondary batteries include a positive electrode, a negative electrode, and an electrolyte housed inside an exterior member. In recent years, solid-state batteries, which are secondary batteries that include a solid electrolyte instead of a liquid or gel electrolyte containing an organic solvent, have been developed (see, for example, Patent Document 1 and Non-Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 131181 [Non-patent literature]

[0004] [Non-Patent Document 1] “Influence of Li2O-B2O3 glass on ionic migration and interfacial properties of La2 / 3xLi3xTiO3 solid electrolyte” Hui Zhang et al., Journalof Alloys and Compounds, 704, 109 (2020) [Non-patent document 2] “Garnet-Based All-Ceramic Lithium Battery Enabled by Li2.985B0.005OCl Solder” Wuliang Feng et al., iScience, 23, 101071 (2020) Summary of the Invention

[0005] As described in the above-mentioned prior art documents, various studies have been conducted to improve the performance of solid-state batteries, but there is still room for improvement in the performance of solid-state batteries.

[0006] Therefore, a solid electrolyte for solid state batteries with excellent performance is desired.

[0007] A solid electrolyte for a solid battery according to one embodiment of the present disclosure includes a first solid electrolyte portion with a perovskite structure having a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less, and a second solid electrolyte portion with an inverse perovskite structure having a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less.

[0008] According to one embodiment of the present disclosure, a solid electrolyte for a solid-state battery combines a first solid electrolyte portion having a perovskite structure with a second solid electrolyte portion having an inverse perovskite structure. The first and second solid electrolyte portions have similar lattice constants, resulting in the formation of lattice-matched ionic bonds. This suppresses the generation of grain boundaries, improving ionic conductivity. Furthermore, when applied to a solid-state battery, the solid electrolyte can achieve excellent performance, such as excellent charge-discharge cycle characteristics.

[0009] Note that the effects of the present disclosure are not necessarily limited to the effects described here, but may be any of a series of effects related to the present disclosure described below. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a cross-sectional view showing a structural example of a solid electrolyte according to a first embodiment of the present disclosure. [Figure 2] FIG. 2 is a schematic cross-sectional view showing the configuration of a battery package according to a second embodiment of the present disclosure. [Figure 3] FIG. 3 is a cross-sectional view illustrating the configuration of the solid-state battery shown in FIG. [Figure 4] FIG. 4 is an enlarged SEM image of a portion of the solid electrolyte layer of Comparative Example 5. As shown in FIG. [Figure 5] FIG. 5 is an enlarged SEM image of a portion of the solid electrolyte layer of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, an embodiment of the present disclosure will be described in detail with reference to the drawings. The description will be made in the following order. 0. Overview of this Disclosure 1. First embodiment 1.1 Composition of solid electrolyte for solid-state batteries 1.2 Manufacturing method of solid electrolyte for solid-state batteries 1.3 Functions and effects of solid electrolytes for solid-state batteries 2. Second embodiment 2.1 Battery package 2.2 Solid state batteries 2.3 Covering 2.4 Battery package manufacturing method 2.5 Action and effect 3. Battery package applications 4. Working Example In addition, the "solid-state battery" in the present disclosure refers to a battery whose components are solid. For example, the "solid-state battery" in the present disclosure is a stacked solid-state battery formed by stacking multiple layers. The multiple layers are made of, for example, a sintered body. The "solid-state battery" in the present disclosure includes not only secondary batteries that can be repeatedly charged and discharged, but also primary batteries that can only be discharged.

[0012] [0. Summary of this Disclosure] First, an overview of the present disclosure will be described. Various studies have been conducted to improve the performance of solid-state batteries. Because solid-state batteries contain a solid electrolyte, they generally have superior high-temperature resistance and higher safety compared to batteries that use liquid electrolytes.

[0013] However, inorganic solid electrolytes are generally in the form of particles, and lithium must move across the interfaces between the solid electrolyte particles. Therefore, even if a material has high lithium ion conductivity (bulk conductivity) within the particles, the lithium ion conductivity at the particle interfaces (grain boundary conductivity) is likely to decrease. For example, oxide solid electrolytes with a perovskite-type solid structure (such as LixLayTiO3) have a low lithium ion conductivity of 10 -3 Although it exhibits excellent bulk conductivity exceeding 1000 S / cm, the decrease in grain boundary conductivity is more pronounced than with other solid electrolytes. To reduce the grain boundary resistance, it is necessary to form clean crystal interfaces by high-temperature sintering at 1350°C or higher, i.e., to thermally bond the particles together to form polycrystals. The need for such high-temperature sintering is a major obstacle to practical application.

[0014] In the above-mentioned Non-Patent Document 1, by adding Li2O-B2O3 mixed glass to LixLayTiO3 and firing it, the sintering temperature is reduced to 1250°C. However, the sintering temperature is still high at 1250°C, which is not suitable for practical use.

[0015] In addition, in the above-mentioned Non-Patent Document 2, solid electrolyte particles having a garnet structure (Li7La3Zr2O 12 The solid electrolyte of Non-Patent Document 2 is made by mixing a garnet-type solid electrolyte (Li3OCl) with a low-melting-point antiperovskite structure, melting the antiperovskite-type solid electrolyte, and bringing it into contact with the garnet-type solid electrolyte, thereby forming a mixed solid electrolyte layer with small voids. -4 An ionic conductivity of 1000 S / cm was obtained. However, the inventors' investigations revealed that cracks occurred at the interface between the garnet-type solid electrolyte and the antiperovskite-type solid electrolyte during charge-discharge cycles, resulting in a decrease in ionic conductivity. Furthermore, it was confirmed that short-circuiting, which is thought to be the effect of the cracks, also occurred.

[0016] Furthermore, in the above Patent Document 1, oxide solid electrolyte particles having a garnet structure (Li7La3Zr2O 12A mixed solid electrolyte layer of lithium halide hydrate (LiI 3H2O) is disclosed. In this mixed solid electrolyte layer, -3 However, oxide solid electrolytes react with water to easily generate highly resistive LiOH and LiOH·H2O at the interface, which reduces the interfacial conductivity.

[0017] In view of the above circumstances, the present applicant proposes a solid electrolyte for solid batteries having superior performance, such as higher ionic conductivity, and a solid battery using the same.

[0018] 1. First Embodiment 1.1 Composition of solid electrolyte for solid-state batteries A solid electrolyte for a solid battery according to a first embodiment of the present disclosure will be described with reference to FIG. 1. FIG. 1 is a schematic cross-sectional view illustrating a structural example of a solid electrolyte for a solid battery. The solid electrolyte for a solid battery is a mixture including a first solid electrolyte portion 31 and a second solid electrolyte portion 32. The first solid electrolyte portion 31 has a perovskite structure. Meanwhile, the second solid electrolyte portion 32 has an inverse perovskite structure. As shown in FIG. 1, the first solid electrolyte portion 31 is made of a plurality of electrolyte particles, and the second solid electrolyte portion 32 is provided so as to fill the gaps between the plurality of first solid electrolyte portions 31. The second solid electrolyte portion 32 is formed by, for example, permeating a molten lithium salt having an inverse perovskite structure into the gaps between the plurality of first solid electrolyte portions 31 and then crystallizing the molten lithium salt. The second solid electrolyte portion 32 may be meltable at a temperature below 400°C.

[0019] It is desirable that the lattice constant of the crystal of the first solid electrolyte portion 31 having a perovskite structure and the lattice constant of the crystal of the second solid electrolyte portion 32 having an inverse perovskite structure are similar to each other. In the perovskite structure and the inverse perovskite structure, positively charged cations and negatively charged anions are arranged in opposite directions. Therefore, if the lattice constants of the perovskite structure and the inverse perovskite structure are similar, positive and negative charges will be adjacent when the two structures come into contact. As a result, ionic bonds are formed in a lattice-matched state with little misalignment of ions, resulting in a very clean interface between the first solid electrolyte portion 31 and the second solid electrolyte portion 32. A clean interface here refers to an interface in an epitaxial state (lattice-matched state) with very few structural defects. Furthermore, the lattice-matched state refers to a state in which the ratio of the lattice constant of the anti-perovskite structure to the lattice constant of the perovskite structure is 0.9 or more and 1.1 or less. It is particularly desirable that the ratio of the lattice constant of the anti-perovskite structure to the lattice constant of the perovskite structure be 0.95 or more and 1.05 or less.

[0020] The first solid electrolyte portion 31 and the second solid electrolyte portion 32 may each have a lattice constant that is an integer multiple of, for example, 3.8 Å or more and 4.1 Å or less. Specifically, the first solid electrolyte portion 31 may be Li 0.33 La 0.56 TiO3, and the second solid electrolyte portion 32 is Li3OCl, Li2(OH)Cl, or Li2(OH)Cl 0.9 F 0.1 It would be good. 0.33 La 0.56 The lattice constant of TiO3 is 3.92 Å, and the lattice constant of Li3OCl, Li2(OH)Cl, and Li2(OH)Cl 0.9 F 0.1 The lattice constants of the first solid electrolyte portion 31 and Li 0.33 La 0.56Part or all of the Ti (titanium) in TiO3 is replaced by Nb (niobium), Ta (tantalum), Zr (zirconium) or Hf (hafnium), and Li 0.33 La 0.56 The second solid electrolyte portion 32 may be at least one of TiO in which part or all of the La (lanthanum) is substituted with Pr (praseodymium) or Nd (neodymium). The second solid electrolyte portion 32 may be at least one of LiOCl and Li(OH)Cl in which part or all of the Cl is substituted with F (fluorine), Br (bromine), or I (iodine).

[0021] <1.2 Manufacturing method of solid electrolyte for solid-state battery> Next, an example of a method for producing a solid electrolyte for a solid battery will be described. First, a first solid electrolyte powder to be the first solid electrolyte portion 31, a second solid electrolyte powder to be the second solid electrolyte portion 32, and an organic binder are kneaded to produce a kneaded powder. Next, the kneaded powder is heated and compression-molded using a hot isostatic pressing (HIP) method or the like to produce a compression-molded body. At this time, it is desirable to perform compression molding while heating at a temperature at which the second solid electrolyte powder melts (for example, a temperature of 200°C or higher but lower than 400°C). This heated compression molding removes water from the kneaded powder and ionically bonds the first solid electrolyte portion 31 and the second solid electrolyte portion 32 in a lattice-matched state. As a result of the above, a solid electrolyte for a solid battery according to this embodiment is obtained.

[0022] <1.3 Functions and effects of solid electrolytes for solid-state batteries> This solid electrolyte for solid batteries achieves excellent lattice matching by combining a first solid electrolyte portion 31 having a perovskite structure with a second solid electrolyte portion 32 having an inverse perovskite structure. In this solid electrolyte for solid batteries, the first solid electrolyte portion 31 is dispersed and incorporated into the second solid electrolyte portion 32, resulting in almost no grain boundaries in the second solid electrolyte portion 32. Furthermore, cracking and delamination at the junction between the first solid electrolyte portion 31 and the second solid electrolyte portion 32 are suppressed. Furthermore, since this solid electrolyte for solid batteries is dehydrated during its manufacturing process, even when an oxide is used for the first solid electrolyte portion 31, the generation of highly resistive LiOH or LiOH·H2O, which can cause a decrease in interfacial conductivity, is suppressed. Therefore, this solid electrolyte for solid batteries achieves high ionic conductivity, enabling rapid charging and high output when used in solid-state batteries. Furthermore, because of the excellent lattice matching, its use as a solid electrolyte layer in solid-state batteries results in excellent charge / discharge cycle characteristics.

[0023] 2. Second Embodiment <2.1 Battery package 100> Next, a battery package 100 according to a second embodiment of the present disclosure will be described. FIG. 2 is a schematic cross-sectional view illustrating the overall configuration of the battery package 100. The battery package 100 includes a solid-state battery 101 and a covering 102 that covers the solid-state battery 101. The covering 102 protects the solid-state battery 101 from the external environment. The covering 102 prevents, for example, water vapor from penetrating into the solid-state battery 101. The solid-state battery 101 will be described below, followed by the covering 102. "Water vapor" here refers to moisture, such as water vapor in the atmosphere, and in a preferred embodiment, refers to moisture that includes not only water vapor in gas form but also liquid water. Preferably, such a moisture-impermeable solid-state battery 101 is packaged to be suitable for substrate mounting, particularly for surface mounting.

[0024] <2.2 Solid state battery 101> FIG. 3 is a schematic cross-sectional view illustrating the configuration of a solid-state battery 101. As illustrated in FIGS. 2 and 3, the solid-state battery 101 includes a laminate 5, a positive electrode terminal 6, and a negative electrode terminal 7. The positive electrode terminal 6 and the negative electrode terminal 7 are disposed opposite each other with the laminate 5 interposed therebetween. As illustrated in FIG. 4, the laminate 5 includes a positive electrode layer 10, a negative electrode layer 20, and a solid electrolyte layer 30 stacked in the Z-axis direction. The solid electrolyte layer 30 is interposed between the positive electrode layer 10 and the negative electrode layer 20 in the Z-axis direction, which is the stacking direction. Specifically, the solid-state battery 101 has a structure in which a unit U, which includes a negative electrode layer 20, a solid electrolyte layer 30, a positive electrode layer 10, and a solid electrolyte layer 30 stacked in this order, is repeatedly stacked in the Z-axis direction. Note that FIG. 3 illustrates the solid-state battery 101 including two units U, but the solid-state battery 101 is not limited to this configuration and may include three or more units U. The solid-state battery 101 may further include blank layers 41 and 42, which are electronic insulating layers. The blank layer 41 is provided in the same layer as a part of the positive electrode layer 10. The blank layer 42 is provided in the same layer as a part of the negative electrode layer 20.

[0025] The positive electrode layer 10 and the negative electrode layer 20 may contain a conductive additive. Examples of the conductive additive that may be contained in the positive electrode layer 10 and the negative electrode layer 20 include at least one of metal materials such as silver, palladium, gold, platinum, copper, and nickel, and carbon. The conductive additive contained in the positive electrode layer 10 and the conductive additive contained in the negative electrode layer 20 may be the same or different.

[0026] (Positive electrode layer 10) The positive electrode layer 10 is an electrode layer containing at least a positive electrode active material. In the solid state battery 101 shown in FIG. 3, the positive electrode layer 10 has a laminated structure including a positive electrode current collector 11 and a pair of positive electrode active material layers 12 and 13.

[0027] The positive electrode current collector 11 is, for example, a metal foil such as an aluminum foil. Although Fig. 3 illustrates an example in which the positive electrode layer 10 includes the positive electrode current collector 11, the positive electrode current collector 11 is not an essential component. The positive electrode layer 10 may include either the positive electrode active material layer 12 or the positive electrode active material layer 13 without including the positive electrode current collector 11.

[0028] (Cathode active material layer 12, 13) The positive electrode active material layers 12 and 13 contain a positive electrode active material as a main component. The positive electrode active material layer 12 is provided on the upper surface of the positive electrode current collector 11, and the positive electrode active material layer 13 is provided on the lower surface of the positive electrode current collector 11.

[0029] The positive electrode active material contained in the positive electrode active material layers 12, 13 is a material that participates in the absorption and release of ions in the solid-state battery 101 and in the transfer of electrons to and from the external circuit. Ions move between the positive electrode layer 10 and the negative electrode layer 20 via the solid electrolyte (i.e., ion conduction). The absorption and release of ions in the positive electrode active material is accompanied by oxidation or reduction of the positive electrode active material. Electrons or holes for such an oxidation-reduction reaction are transferred from the external circuit to the positive electrode terminal 6 or the negative electrode terminal 7, and then to the positive electrode layer 10 or the negative electrode layer 20, thereby allowing charging and discharging to proceed. The positive electrode active material layers 12, 13 contain, for example, lithium ions, sodium ions, protons (H + ), potassium ions (K + ), magnesium ions (Mg 2+ ), aluminum ions (Al 3+ ), silver ions (Ag + ), fluoride ion (F - ) or chloride ions (Cl - In other words, the solid-state battery 101 is preferably an all-solid-state secondary battery in which charging and discharging are performed by the ions moving between the positive electrode layer 10 and the negative electrode layer 20 via the solid electrolyte.

[0030] (Cathode active material) The positive electrode active material contained in the positive electrode layer 10 may be at least one selected from the group consisting of a lithium-containing phosphate compound having a Nasicon structure, a lithium-containing phosphate compound having an olivine structure, a lithium-containing layered oxide, and a lithium-containing oxide having a spinel structure. An example of a lithium-containing phosphate compound having a Nasicon structure is Li3V2(PO4)3. An example of a lithium-containing phosphate compound having an olivine structure is Li3Fe2(PO4)3, LiFePO4, LiMnPO4, LiFe 0.6 Mn 0.4 Examples of lithium-containing layered oxides include LiCoO2, LiCo 1 / 3 Ni 1 / 3 Mn 1 / 3 O2, LiCo 0.8 Ni 0.15 Al 0.05 Examples of lithium-containing oxides having a spinel structure include LiMn2O4, LiNi 0.5 Mn 1.5 Examples include O4.

[0031] In addition, the positive electrode active material capable of absorbing and releasing sodium ions may be at least one selected from the group consisting of sodium-containing phosphate compounds having a Nasicon structure, sodium-containing phosphate compounds having an olivine structure, sodium-containing layered oxides, and sodium-containing oxides having a spinel structure.

[0032] (negative electrode layer 20) The negative electrode layer 20 is an electrode layer containing at least a negative electrode active material. The negative electrode layer 20 may have a negative electrode current collector. The negative electrode current collector is, for example, a metal foil such as a copper foil.

[0033] (Negative electrode active material) The anode active material contained in the anode layer 20, like the cathode active material contained in the cathode layer 10, is a material that participates in the absorption and release of ions in the solid-state battery 101 and in the transfer of electrons to and from the external circuit. Ions move between the cathode layer 10 and the anode layer 20 via the solid electrolyte layer 30 (i.e., ion conduction). The absorption and release of ions in the anode active material is accompanied by oxidation or reduction of the anode active material. Electrons or holes for such oxidation-reduction reactions are transferred from the external circuit to the cathode terminal 6 or the anode terminal 7, and then to the cathode layer 10 or the anode layer 20, thereby allowing charging and discharging to proceed. The anode active material may contain, for example, lithium ions, sodium ions, protons (H + ), potassium ions (K + ), magnesium ions (Mg 2+ ), aluminum ions (Al 3+ ), silver ions (Ag + ), fluoride ion (F - ) or chloride ions (Cl - ) can be absorbed and released. Examples of the negative electrode active material contained in the negative electrode layer 20 include at least one selected from the group consisting of an oxide containing at least one element selected from the group consisting of Ti, Si, Sn, Cr, Fe, Nb, and Mo, a graphite-lithium compound, a lithium alloy, a lithium-containing phosphate compound having a Nasicon structure, a lithium-containing phosphate compound having an olivine structure, and a lithium-containing oxide having a spinel structure. An example of a lithium alloy is Li-Al. Examples of lithium-containing phosphate compounds having a Nasicon structure are Li3V2(PO4)3 and LiTi2(PO4)3. Examples of lithium-containing phosphate compounds having an olivine structure are Li3Fe2(PO4)3 and LiCuPO4. An example of a lithium-containing oxide having a spinel structure is Li4Ti5O 12 etc.

[0034] In addition, the negative electrode active material capable of absorbing and releasing sodium ions may be at least one selected from the group consisting of sodium-containing phosphate compounds having a Nasicon structure, sodium-containing phosphate compounds having an olivine structure, and sodium-containing oxides having a spinel structure.

[0035] (Solid electrolyte layer 30) The solid electrolyte layer 30 forms a layer capable of conducting, for example, lithium ions, between the positive electrode layer 10 and the negative electrode layer 20. The solid electrolyte for a solid battery described in the first embodiment can be used as the solid electrolyte layer 30.

[0036] (Positive terminal 6 and negative terminal 7) The positive electrode terminal 6 and the negative electrode terminal 7 are external connection terminals for connecting the laminate 5 to an external device. The positive electrode terminal 6 and the negative electrode terminal 7 are preferably provided as end surface electrodes on the side surfaces of the laminate 5. That is, the positive electrode terminal 6 and the negative electrode terminal 7 extend along the Z-axis direction, which is the stacking direction of the laminate 5. In FIG. 3, the positive electrode terminal 6 and the negative electrode terminal 7 are arranged to face each other in the X-axis direction. As shown in FIG. 3, the positive electrode terminal 6 is electrically connected to the end surface of the positive electrode current collector 11 of the positive electrode layer 10. The negative electrode terminal 7 is electrically connected to the end surface of the negative electrode layer 20. The positive electrode terminal 6 and the negative electrode terminal 7 are preferably made of a material having high conductivity. Examples of materials for the positive electrode terminal 6 and the negative electrode terminal 7 include at least one selected from the group consisting of gold, silver, platinum, aluminum, tin, nickel, copper, manganese, cobalt, iron, titanium, and chromium. However, the constituent materials of the positive electrode terminal 6 and the negative electrode terminal 7 are not limited to those mentioned above.

[0037] (Margin layers 41, 42) The marginal layer 41 has marginal portions 411 to 413. The marginal portion 411 is in the same layer as the positive electrode current collector 11 and is provided between the positive electrode current collector 11 and the negative electrode terminal 7. The marginal portion 412 is in the same layer as the positive electrode active material layer 12 and is provided between the positive electrode active material layer 12 and the positive electrode terminal 6 and between the positive electrode active material layer 12 and the negative electrode terminal 7. The marginal portion 413 is in the same layer as the positive electrode active material layer 13 and is provided between the positive electrode active material layer 13 and the positive electrode terminal 6 and between the positive electrode active material layer 13 and the negative electrode terminal 7. The marginal layer 42 is in the same layer as the negative electrode layer 20 and is provided between the negative electrode layer 20 and the positive electrode terminal 6.

[0038] Examples of materials constituting the marginal portions 411 to 413 of the marginal layer 41 and the marginal layer 42 include materials having electronic insulation properties (hereinafter simply referred to as insulating materials).

[0039] Examples of insulating materials include glass and ceramic. Examples of glass materials include, but are not limited to, at least one selected from the group consisting of soda-lime glass, potash glass, borate glass, borosilicate glass, barium borosilicate glass, zinc borate glass, barium borate glass, bismuth borosilicate glass, bismuth zinc borate glass, bismuth silicate glass, phosphate glass, aluminophosphate glass, and zinc phosphate glass. Examples of ceramic materials include, but are not limited to, at least one selected from the group consisting of aluminum oxide (Al2O3), boron nitride (BN), silicon dioxide (SiO2), silicon nitride (Si3N4), zirconium oxide (ZrO2), aluminum nitride (AlN), silicon carbide (SiC), and barium titanate (BaTiO3).

[0040] The insulating material constituting the blank layers 41, 42 may contain a solid electrolyte. In this case, the solid electrolyte contained in the insulating material is preferably the same material as the solid electrolyte contained in the solid electrolyte layer 30. This is because such a configuration can further improve the bonding between the blank layers 41, 42 and the solid electrolyte layer 30.

[0041] <2.3 Covering portion 102> 2, the covering portion 102 of the battery package 100 has a support substrate 102A, a covering insulating film 102B, and a covering inorganic film 102C. In the battery package 100, the solid-state battery 101 is entirely surrounded by the covering portion 102. In other words, the covering portion 102 is provided so that the solid-state battery 101 is not exposed to the outside.

[0042] (Support board 102A) The support substrate 102A is a plate-shaped member that supports the solid-state battery 101. The support substrate 102A has a surface 102S that faces the bottom surface 101B, which is the main surface of the solid-state battery 101. The support substrate 102A may be a resin substrate or a ceramic substrate. In a preferred embodiment, the support substrate 102A is a ceramic substrate. The support substrate 102A contains ceramic as a main component. A ceramic substrate is preferable because it has excellent water vapor prevention properties and excellent heat resistance. A ceramic substrate can be obtained, for example, by firing a green sheet laminate. Specifically, the ceramic substrate may be, for example, an LTCC (Low Temperature Co-fired Ceramics) substrate or an HTCC (High Temperature Co-fired Ceramic) substrate. By way of example only, the thickness of the support substrate 102A is 20 μm to 1000 μm, for example, 100 μm to 300 μm.

[0043] (Coating insulation film 102B) The coated insulating film 102B is a layer provided so as to cover at least the top surface 101A and the side surface 101C of the solid-state battery 101. As shown in FIG. 2, the solid-state battery 101 provided on the support substrate 102A is entirely enclosed by the coated insulating film 102B. In a preferred embodiment, the coated insulating film 102B is provided so as to cover the entire top surface 101A and the side surface 101C of the solid-state battery 101. Of the two main surfaces constituting the solid-state battery 101, the one positioned relatively lower is the bottom surface 101B. Therefore, the top surface 101A is the main surface located opposite the support substrate 102A. Therefore, the coated insulating film 102B may cover all surfaces of the solid-state battery 101 except for the bottom surface 101B. The coated insulating film 102B is made of, for example, a resin material capable of blocking water vapor. The coated insulating film 102B, in combination with the coated inorganic film 102C, forms a suitable water vapor barrier. Examples of materials used for the coated insulating film 102B include epoxy resins, silicone resins, and liquid crystal polymers. By way of example only, the thickness of the coated insulating film 102B is 30 μm or more and 1000 μm or less, and may be, for example, 50 μm or more and 300 μm or less.

[0044] (Coated inorganic film 102C) The coated inorganic film 102C is provided to cover the coated insulating film 102B. Since the coated inorganic film 102C is positioned on the coated insulating film 102B, together with the coated insulating film 102B, it has a shape that largely envelops the solid-state battery 101 on the support substrate 102A as a whole. The material of the coated inorganic film 102C is not particularly limited as long as it is an inorganic material. The coated inorganic film 102C may be metal, glass, oxide ceramic, or a mixture thereof. In a preferred embodiment, the coated inorganic film 102C contains a metal component. That is, the coated inorganic film 102C may be a metal thin film. By way of example only, the thickness of the coated inorganic film 102C is 0.1 μm or more and 100 μm or less, for example, 1 μm or more and 50 μm or less. The coated inorganic film 102C may be a dry-plated film. The dry-plated film referred to here is a film obtained by a vapor-phase method such as physical vapor deposition (PVD) or chemical vapor deposition (CVD), and is a thin film having an extremely thin thickness on the order of nanometers or micrometers. A thin dry-plated film contributes to the miniaturization and thinning of the battery package 100. The dry-plated film may contain at least one metal selected from the group consisting of aluminum (Al), nickel (Ni), palladium (Pd), silver (Ag), tin (Sn), gold (Au), copper (Cu), titanium (Ti), platinum (Pt), silicon (Si), and stainless steel. A dry-plated film made of such components is chemically and thermally stable, resulting in a solid-state battery 101 with excellent chemical resistance, weather resistance, and heat resistance, and thus improved long-term reliability.

[0045] In the battery package 100 shown in FIG. 3, the support substrate 102A is a terminal substrate provided with substrate wiring 8 including external terminals for connecting the solid-state battery 101 to an external device. The substrate wiring 8 in the support substrate 102A serving as a terminal substrate is not particularly limited as long as it allows electrical connection between the upper and lower surfaces of the support substrate 102A. In FIG. 2, the support substrate 102A is provided with substrate wiring 8 including a via 8A and a pair of lands 8B and 8C. The land 8B is exposed on the upper surface of the support substrate 102A and is electrically connected to the positive electrode terminal 6 or the negative electrode terminal 7. The land 8C is exposed on the lower surface of the support substrate 102A. The via 8A penetrates the support substrate 102A to connect the land 8B and the land 8C.

[0046] <2.4 Manufacturing method> Next, a brief description will be given of a method for manufacturing the battery package 100 of the present disclosure. The battery package 100 can be produced, for example, by a step of manufacturing the solid-state battery 101 and a step of packaging the solid-state battery 101.

[0047] (Process for manufacturing the solid-state battery 101) In manufacturing the laminate 5 of the solid-state battery 101, a printing method such as a screen printing method, a green sheet method using a green sheet, or a combination of these methods can be used.

[0048] The following description will be given using one manufacturing method as an example, but the present disclosure is not limited to the manufacturing method described below. Furthermore, the chronological order of the following descriptions is merely for the convenience of explanation, and the present disclosure is not limited to these details.

[0049] First, the positive electrode layer 10 is fabricated. Specifically, after preparing a positive electrode current collector 11, positive electrode active material particles, a resin, and a solvent are mixed to form a positive electrode slurry. Next, the positive electrode slurry is applied to both sides of the positive electrode current collector 11, and the applied positive electrode slurry is dried to form a positive electrode green sheet. Furthermore, the fabricated positive electrode green sheet is impregnated with a molten positive electrode solid electrolyte by dropping it, for example. Examples of the molten positive electrode solid electrolyte include Li2CO3, Li2SO4, Li3BO3, Li3OCl, Li2OHCl, and Li2(OH)Cl. 0.9 F 0.1 ,Li2(OH)Cl 0.9 Br 0.1 and Li2(OH)Cl 0.9 I 0.1 It is preferable to use at least one of the following: In this way, the positive electrode layer 10 is obtained.

[0050] Next, the negative electrode layer 20 is fabricated. Specifically, negative electrode active material particles, a resin, and a solvent are mixed to form a negative electrode slurry. Subsequently, the negative electrode slurry is applied to a film, and the applied negative electrode slurry is dried to form a negative electrode green sheet. Furthermore, the fabricated negative electrode green sheet is impregnated with a molten negative electrode solid electrolyte by, for example, dropping it. Examples of the molten negative electrode solid electrolyte include Li2CO3, Li2SO4, Li3BO3, Li3OCl, Li2OHCl, and Li2(OH)Cl. 0.9 F 0.1 ,Li2(OH)Cl 0.9 Br 0.1 and Li2(OH)Cl 0.9 I 0.1 It is preferable to use at least one of the following: In this way, the negative electrode layer 20 is obtained.

[0051] Next, the solid electrolyte layer 30 is fabricated according to the procedure described in the first embodiment.

[0052] Furthermore, an insulating material, a binder, an organic binder, a solvent, and optional additives are mixed together to prepare an insulating paste.

[0053] Next, the positive electrode layer 10, the solid electrolyte layer 30, the negative electrode layer 20, and the solid electrolyte layer 30 are stacked in this order to form a laminate structure. This laminate structure corresponds to one unit U shown in FIG. 4. When fabricating this laminate structure, an insulating paste is applied to the areas where the blank layers 41 and 42 will be formed. The laminate structure is impregnated with a molten solid electrolyte for the solid electrolyte layer by, for example, dropping it, and then dried. This impregnates the sintered solid electrolyte with the solid electrolyte, resulting in the solid electrolyte layer 30. The molten solid electrolyte for the solid electrolyte layer may be a lithium molten salt containing at least one of Li2CO3, Li2SO4, Li3BO3, Li3OCl, and Li2OHCl. The dried laminate structure is compressed by cold isostatic pressing (CIP) or the like to pressure-bond the positive electrode layer 10, the solid electrolyte layer 30, the negative electrode layer 20, and the solid electrolyte layer 30. Finally, the laminate 5 is obtained by firing at a temperature of less than 800° C. in a nitrogen atmosphere.

[0054] Next, a conductive paste is applied to the side surface of the sintered laminate 5 where a portion of the positive electrode layer 10 is exposed. This allows the positive electrode terminal 6 to be formed. Similarly, a conductive paste is applied to the side surface of the sintered laminate 5 where a portion of the negative electrode layer 20 is exposed. This allows the negative electrode terminal 7 to be formed. Note that the positive electrode terminal 6 and the negative electrode terminal 7 do not necessarily have to be formed on the sintered laminate 5, but may be formed on the laminate structure before firing and sintered simultaneously with the laminate structure.

[0055] In this way, the solid state battery 101 can be obtained.

[0056] (Process of packaging the solid-state battery 101) First, the support substrate 102A is prepared. The support substrate 102A can be obtained, for example, by stacking and firing multiple green sheets. The preparation of the support substrate 102A can be performed, for example, in accordance with the preparation of an LTCC substrate. The support substrate 102A has substrate wiring 8 formed thereon, including vias 8A and lands 8B, 8C. Specifically, for example, holes are formed in the green sheets using a punch press or a carbon dioxide laser, and the vias 8A and lands 8B, 8C are formed by filling the holes with a conductive paste material or by using a printing method. Next, a predetermined number of such green sheets are stacked and thermocompression-bonded to form a green sheet laminate, and the green sheet laminate is then fired to obtain the support substrate 102A on which the substrate wiring 8 is formed. The substrate wiring 8 can also be formed after firing the green sheet laminate.

[0057] After preparing the support substrate 102A as described above, the solid-state battery 101 is placed on the support substrate 102A. At this time, the solid-state battery 101 is placed on the support substrate 102A so that the board wiring 8 of the support substrate 102A and the positive electrode terminal 6 and negative electrode terminal 7 of the solid-state battery 101 are electrically connected to each other. Note that a conductive paste containing silver or the like may be applied onto the board wiring 8 of the support substrate 102A, and the conductive paste may be electrically connected to the positive electrode terminal 6 and negative electrode terminal 7, respectively.

[0058] Next, the insulating coating film 102B is formed so as to entirely cover the solid-state battery 101 on the support substrate 102A. When the insulating coating film 102B is made of a resin material, the resin material is applied so as to cover the side surface 101C and the top surface 101A of the solid-state battery 101, and then the resin material is cured to form the insulating coating film 102B. For example, the insulating coating film 102B may be molded by applying pressure to the resin material using a mold of a predetermined shape. Note that the molding of the insulating coating film 102B is not limited to mold molding, and may also be performed using polishing, laser processing, chemical treatment, or the like.

[0059] Next, the inorganic coated film 102C is formed so as to entirely cover the insulating coated film 102B. Specifically, for example, the inorganic coated film 102C may be formed by dry plating.

[0060] By going through the steps described above, a battery package 100 can be obtained in which the solid state battery 101 mounted on the support substrate 102A is entirely covered with the insulating coating film 102B and the inorganic coating film 102C.

[0061] <2.5 Effects> According to the battery package 100 including the solid-state battery 101 of this embodiment, the laminate 5 of the solid-state battery 101 has a solid electrolyte layer 30 made of the solid electrolyte for solid-state batteries described in the first embodiment. Therefore, a good lattice matching state can be obtained in the solid electrolyte layer 30. Since the solid electrolyte layer 30 has high ionic conductivity, the solid-state battery 101 and the battery package 100 having this can achieve better performance, such as being able to be rapidly charged and obtaining high output.

[0062] [3. Battery package applications] Next, uses (application examples) of the battery package including the above-described solid-state battery will be described.

[0063] The use of the battery package is not particularly limited as long as it is used mainly in machines, devices, instruments, apparatuses, and systems (assemblies of multiple devices, etc.) that can use solid-state batteries as a driving power source or a power storage source for power accumulation. The battery package used as a power source may be a main power source or an auxiliary power source. A main power source is a power source that is used preferentially regardless of the presence or absence of other power sources. An auxiliary power source may be a power source used in place of the main power source, or a power source that can be switched from the main power source as needed. When the battery package is used as an auxiliary power source, the type of main power source is not limited to one equipped with a solid-state battery.

[0064] Specific examples of uses for battery packages are as follows: Electronic devices (including portable electronic devices) such as video cameras, digital still cameras, mobile phones, notebook computers, cordless phones, headphone stereos, portable radios, portable televisions, and portable information terminals. Portable household appliances such as electric shavers. Storage devices such as backup power supplies and memory cards. Power tools such as power drills and power saws. Battery packs installed in notebook computers and the like as removable power sources. Medical electronic devices such as pacemakers and hearing aids. Electric vehicles such as electric cars (including hybrid cars). Power storage systems such as home battery systems that store power in preparation for emergencies. It is also possible to use multiple battery packages as a battery module.

[0065] The battery module is effectively applied to relatively large equipment such as electric vehicles, power storage systems, and power tools. An electric vehicle is a vehicle that operates (runs) using a battery module as its driving power source, and may also be an automobile (such as a hybrid automobile) that also has a driving source other than a battery package equipped with solid-state batteries. A power storage system is a system that uses a battery package as a power storage source. In a home power storage system, power is stored in a secondary battery, which is the power storage source, and this power can be used to power household electrical appliances, etc.

[0066] 4. Working Example An embodiment of the present disclosure will now be described.

[0067] Example 1 As will be described below, the solid state battery 101 shown in FIG. 3 was fabricated, and then its battery characteristics were evaluated.

[0068] (Fabrication of Positive Electrode Layer 10) First, a 15 μm thick aluminum foil was prepared as the positive electrode current collector 11. Next, a positive electrode mixture was obtained by mixing lithium nickel cobalt aluminum oxide (LiNiCoAlO2) as the positive electrode active material, PVDF (polyvinylidene fluoride) as the positive electrode binder, and a conductive additive containing a mixture of carbon black, acetylene black, and ketjen black. The mixture ratio of the positive electrode active material, the positive electrode binder, and the conductive additive was 95:3:2. Next, the positive electrode mixture was added to NMP (N-methyl-2-pyrrolidone) as the organic solvent, and the organic solvent containing the positive electrode mixture was stirred to prepare a paste-like positive electrode slurry. Stirring was performed using a hybrid mixer at a rotation speed of 2000 rpm for 3 minutes. Next, a coating device was used to apply the positive electrode slurry to predetermined regions on both sides of the positive electrode current collector 11, and the positive electrode slurry was then dried to form positive electrode green sheets on both sides of the positive electrode current collector 11. Furthermore, molten Li2(OH)Cl was added as a lithium molten salt to the prepared positive electrode green sheets. 0.9 F 0.1 The positive electrode layer 10 was thus obtained.

[0069] (Fabrication of negative electrode layer 20) Lithium titanium oxide (Li4Ti5O 12A negative electrode mixture was obtained by mixing the negative electrode active material, the negative electrode binder, and a conductive additive containing a mixture of polyimide, carbon black, acetylene black, and ketjen black as a negative electrode binder. The mixing ratio of the negative electrode active material, the negative electrode binder, and the conductive additive was 90:5:5. Next, the negative electrode mixture was added to NMP (N-methyl-2-pyrrolidone) as an organic solvent, and the organic solvent containing the negative electrode mixture was stirred to prepare a paste-like negative electrode slurry. The stirring was performed using a hybrid mixer at a rotation speed of 2000 rpm for 3 minutes. Next, the negative electrode slurry was applied to a release film made of polyethylene terephthalate (PET) using a coating device, and the negative electrode slurry was dried to form a negative electrode green sheet on the release film. Furthermore, molten Li2(OH)Cl was added as a lithium molten salt to the prepared negative electrode green sheet. 0.9 F 0.1 The negative electrode layer 20 was thus obtained.

[0070] (Fabrication of solid electrolyte layer 30) The first solid electrolyte powder is Li with a perovskite structure and a lattice constant of 3.92 Å. 0.33 La 0.55 TiO3 and Li2(OH)Cl with a lattice constant of 3.91 Å as the second solid electrolyte powder. 0.9 F 0.1 The powder mixture was then heated and compressed by hot isostatic pressing (HIP) to produce a compact. 0.9 F 0.1 The mixture was compression molded while being heated at 270° C., which is lower than the melting temperature of 285° C. Thus, the solid electrolyte layer 30 was obtained.

[0071] (Production of laminate 5) Next, the positive electrode layer 10, the solid electrolyte layer 30, the negative electrode layer 20, and the solid electrolyte layer 30 prepared as above were sequentially stacked to prepare a laminate structure. The laminate structure was pressed and fixed at 0.5 MPa using a jig, and fired at 270°C for 1 hour in a nitrogen atmosphere to obtain a laminate 5.

[0072] Next, a conductive paste was applied to the side surface of the laminate 5 where a portion of the positive electrode layer 10 was exposed, thereby forming a positive electrode terminal 6. A conductive paste was applied to the side surface of the laminate 5 where a portion of the negative electrode layer 20 was exposed, thereby forming a negative electrode terminal 7.

[0073] In this way, the solid state battery 101 was obtained.

[0074] (Evaluation of battery characteristics) The battery characteristics of the solid-state battery 101 were evaluated, and the results shown in Table 1 were obtained. The ionic conductivity [S / cm] of the solid electrolyte layer 30 at 90°C, the cycle capacity retention rate [%] after 100 cycles, and the presence or absence of cracks in the solid electrolyte layer after 100 cycles were evaluated. Specifically, the ionic conductivity [S / cm] was measured using an AC impedance measuring device (manufactured by Solartron, 1260A) at a frequency range of 100 mHz to 1 MHz and an AC amplitude voltage of 100 mV. Regarding the cycle capacity retention rate [%] after 100 cycles, the solid-state battery 101 of Example 1 was charged and discharged in the following manner in an environment of 90°C. First, the battery was charged at a constant current of 0.5 mA until the battery voltage reached 2.6 V, and then discharged at a constant current of 0.5 mA until the voltage reached 0.5 V. This combination of charging and discharging constituted one cycle, and this cycle was repeated 100 times. The ratio of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle was calculated, and this value was defined as the cycle capacity retention rate [%] after 100 cycles. Furthermore, to check for the presence or absence of cracks in the solid electrolyte layer after 100 cycles, the solid battery 101 after 100 cycles was disassembled and the solid electrolyte layer 30 was removed. The removed solid electrolyte layer 30 was fractured with a ceramic cutter, and the fractured surface was polished with a cross-section polisher. The presence or absence of cracks was determined by observing the processed cross section with a scanning electron microscope (SEM).

[0075] [Table 1]

[0076] <Example 2> As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 1, except that Li2(OH)Cl having a lattice constant of 3.91 Å was used as the second solid electrolyte powder in fabricating the solid state electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 1.

[0077] Example 3 As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 1, except that Li3OCl having a lattice constant of 3.91 Å was used as the second solid electrolyte powder in fabricating the solid state electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 1.

[0078] <Comparative Example 1> As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 1, except that the second solid electrolyte powder having an inverse perovskite structure was not mixed in when fabricating the solid state electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 1.

[0079] <Comparative Example 2> As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 1, except that the first solid electrolyte powder having a perovskite structure was not mixed in when fabricating the solid electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 1. The results are also shown in Table 1.

[0080] <Comparative Example 3> As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 2, except that the first solid electrolyte powder having a perovskite structure was not mixed in when fabricating the solid electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 2. The results are also shown in Table 1.

[0081] <Comparative Example 4> As shown in Table 1, a solid state battery 101 was fabricated in the same manner as in Example 3, except that the first solid electrolyte powder having a perovskite structure was not mixed in when fabricating the solid electrolyte layer 30, and then the battery characteristics were evaluated in the same manner as in Example 3. The results are also shown in Table 1.

[0082] <Comparative Example 5> As shown in Table 1, when the solid electrolyte layer 30 was produced, Li7La3Zr2O having a non-perovskite structure was used instead of the first solid electrolyte powder having a perovskite structure.12 Li2(OH)Cl as the second solid electrolyte powder 0.9 F 0.1 A solid-state battery 101 was fabricated in the same manner as in Example 1, except that Li7La3Zr2O was kneaded with Li7La3Zr2O. The battery characteristics were then evaluated in the same manner as in Example 1. The results are also shown in Table 1. 12 has a garnet-type structure with a lattice constant of 12.95 Å.

[0083] <Comparative Example 6> As shown in Table 1, in producing the solid electrolyte layer 30, Li SiO 2 having a non-perovskite structure was used instead of the first solid electrolyte powder having a perovskite structure. 1.07 Al 0.69 Ti 1.46 (PO4)3 as the second solid electrolyte powder, Li2(OH)Cl 0.9 F 0.1 A solid state battery 101 was fabricated in the same manner as in Example 1, except that the Li was kneaded with the Li 1.07 Al 0.69 Ti 1.46 (PO4)3 is a glass-ceramic material with a lattice constant of 8.5 Å.

[0084] [Consideration] As shown in Table 1, Examples 1 to 3 exhibited higher cycle capacity retention rates after 100 cycles than Comparative Examples 1 to 6. This is thought to be because, in all of Comparative Examples 1 to 6, cracks occurred in the solid electrolyte layer after charge-discharge cycling (see FIG. 4), whereas no such cracks occurred in Examples 1 to 3 (see FIG. 5). FIG. 4 is an SEM image of a portion of the solid electrolyte layer of Comparative Example 5, and FIG. 5 is an SEM image of a portion of the solid electrolyte layer of Example 1. The magnifications in both FIGS. 4 and 5 are 2000 times. Furthermore, Examples 1 to 3 exhibited ionic conductivities equal to or higher than those of Comparative Examples 1 to 6. Although the ionic conductivity of Comparative Example 1 was higher than those of Examples 1 to 3, the cycle capacity retention rate after 100 cycles was extremely poor.

[0085] From the above results, it was confirmed that in the solid electrolyte for solid batteries of the present disclosure, by combining the first solid electrolyte portion 31 having a perovskite structure and the second solid electrolyte portion 32 having an inverse perovskite structure, a good lattice matching state is obtained, and good ionic conductivity is obtained. It was also confirmed that cracking and peeling at the joint between the first solid electrolyte portion 31 and the second solid electrolyte portion 32 are suppressed, and stable ionic conductivity is maintained even after repeated charge and discharge.

[0086] The present disclosure has been described above with reference to several embodiments, modifications, and examples, but the configuration of the present disclosure is not limited to the configuration described above and can be modified in various ways.

[0087] Specifically, for example, in the first embodiment, the battery package 100 is described in which the solid-state battery 101 is placed on the support substrate 102A and packaged, but the battery package of the present disclosure is not limited to this form. For example, the battery package may not have a support substrate and may be sealed only by a covering insulating film or a covering inorganic film.

[0088] Furthermore, in the first embodiment, the electrode reactant is lithium, but the electrode reactant is not particularly limited. Therefore, as described above, the electrode reactant may be other alkali metals such as sodium and potassium, or alkaline earth metals such as beryllium, magnesium, and calcium. In addition, the electrode reactant may be other light metals such as aluminum.

[0089] The effects described in this specification are merely examples, and the effects of the present disclosure are not limited to the effects described in this specification. Therefore, other effects may be obtained with respect to the present disclosure.

Claims

1. a first solid electrolyte portion having a perovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; a second solid electrolyte portion having an antiperovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; and The second solid electrolyte portion is Li ２ (OH)Cl, or Li ２ At least one of (OH)Cl in which all or part of Cl is substituted with F (fluorine), Br (bromine) or I (iodine) Solid electrolyte for solid batteries.

2. the first solid electrolyte portion has a plurality of particles; The second solid electrolyte portion is provided between the plurality of particles. The solid electrolyte for a solid battery according to claim 1.

3. The first solid electrolyte portion is Li ０．３３ La ０．５６ TiO ３ or Li ０．３３ La ０．５６ TiO ３ In the above, part or all of Ti (titanium) is replaced by Nb (niobium), Ta (tantalum), Zr (zirconium) or Hf (hafnium), and Li ０．３３ La ０．５６ TiO ３ wherein part or all of the La (lanthanum) is replaced by Pr (praseodymium) or Nd (neodymium).

3. The solid electrolyte for a solid battery according to claim 1.

4. A positive electrode and a negative electrode; a solid electrolyte layer interposed between the positive electrode and the negative electrode; Equipped with The solid electrolyte layer is a first solid electrolyte portion having a perovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; a second solid electrolyte portion having an antiperovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; and The second solid electrolyte portion is Li ２ (OH)Cl, or Li ２ At least one of (OH)Cl in which all or part of Cl is substituted with F (fluorine), Br (bromine) or I (iodine) solid state battery.

5. A solid-state battery; a covering portion that covers the solid-state battery; Equipped with The solid-state battery comprises: A positive electrode and a negative electrode; a solid electrolyte layer interposed between the positive electrode and the negative electrode; Equipped with The solid electrolyte layer is a first solid electrolyte portion having a perovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; a second solid electrolyte portion having an antiperovskite structure with a lattice constant that is an integer multiple of 3.8 Å or more and 4.1 Å or less; and The second solid electrolyte portion is Li ２ (OH)Cl, or Li ２ At least one of (OH)Cl in which all or part of Cl is substituted with F (fluorine), Br (bromine) or I (iodine) Battery package.

Images