Battery

Abstract

The discharge capacity is improved. The battery includes: a positive electrode; a negative electrode having a negative electrode active material layer containing a negative electrode active material and insulating particles; and an electrolyte layer containing a solid electrolyte. The negative electrode active material layer has a first main surface positioned on the electrolyte layer side, and a second main surface positioned on the side facing the first main surface. The negative electrode active material in the negative electrode active material layer is continuous from the first principal surface to the second principal surface. The particles are located on the first main surface of the negative electrode active material layer.

Description

Technical Field

[0001] This invention relates to batteries. Background Technology

[0002] Patent document 1 describes an all-solid-state battery in which microparticles are contained at the boundary between the solid electrolyte layer and the negative electrode layer, and the microparticles contain a sulfide-based solid electrolyte.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent No. 6204671 Summary of the Invention

[0006] The technical problem that the invention aims to solve

[0007] However, in the battery shown in Patent Document 1, the solid electrolyte may be reduced and decomposed due to side reactions of the charge and discharge reaction, resulting in a decrease in discharge capacity.

[0008] This disclosure was made in view of the above-mentioned technical problems, and its purpose is to improve the discharge capacity.

[0009] Solutions for solving technical problems

[0010] One aspect of the battery involves: a positive electrode; a negative electrode having a negative electrode active material layer containing negative electrode active material and insulating particles; and an electrolyte layer containing a solid electrolyte, wherein the negative electrode active material layer has a first main surface located on the side of the electrolyte layer and a second main surface located on the side opposite to the first main surface, wherein the negative electrode active material in the negative electrode active material layer is continuous from the first main surface to the second main surface, and the particles are located on the first main surface of the negative electrode active material layer.

[0011] Invention Effects

[0012] According to the present invention, the discharge capacity can be improved. Attached Figure Description

[0013] Figure 1 This is a schematic cross-sectional view showing an example of the battery according to the first embodiment. Detailed Implementation

[0014] The embodiments of this disclosure will now be described. It should be noted that this disclosure is not limited to these embodiments.

[0015] (First Implementation)

[0016] Figure 1This is a schematic cross-sectional view showing an example of the battery according to the first embodiment. Battery 1 in the first embodiment is an all-solid-state battery with a solid electrolyte, specifically a lithium-ion secondary battery. Figure 1 As shown, battery 1 includes a protective layer 10, a positive electrode 20, a negative electrode 30, and an electrolyte layer 40. Figure 1 In the example, battery 1 has a structure consisting of a sheet-like positive electrode 20, a negative electrode 30, and an electrolyte layer 40 stacked together.

[0017] In the accompanying drawings illustrating this embodiment, the Z direction refers to the stacking direction of the positive electrode 20, the negative electrode 30, and the electrolyte layer 40, and the X direction refers to the direction orthogonal to the Z direction and perpendicular to the X direction. Figure 1 The Y direction is the direction parallel to the cross-section, and it refers to the direction orthogonal to both the X and Z directions. Furthermore, in the description of this embodiment, sometimes one of the X directions is designated as the +X direction and the other as the -X direction. Similarly, sometimes one of the Z directions is designated as the +Z direction and the other as the -Z direction.

[0018] The protective layer 10 is a layer provided for the physical and chemical protection of the battery 1. The protective layer 10 is arranged such that it overlaps with the stack of the positive electrode 20, negative electrode 30, and electrolyte layer 40 when viewed from above in the Z direction. Figure 1 In the example, it is disposed on both sides of the laminate of positive electrode 20, negative electrode 30 and electrolyte layer 40 in the Z direction. The material of protective layer 10 is not particularly limited as long as it is an insulator, such as resin, glass, ceramic, etc.

[0019] The positive electrode 20 has a positive electrode current collector layer 21 and a positive electrode active material layer 22. Figure 1 In this example, the positive electrode 20 has a structure in which the positive electrode active material layer 22 is stacked in the -Z direction of the positive electrode current collector layer 21, but this is just one example. It can also be stacked in the +Z direction of the positive electrode current collector layer 21.

[0020] The positive current collector layer 21 is a conductive layer. Figure 1 In this example, the +X direction end face of the positive electrode current collector layer 21 is exposed and can be connected to the outside. That is, the +X direction end face of the positive electrode current collector layer 21 becomes the positive electrode of the battery 1. The material of the positive electrode current collector layer 21 is not particularly limited as long as it is a conductive material, and examples include metals such as silver, palladium, gold, platinum, aluminum, copper, and nickel, as well as carbon materials.

[0021] The positive electrode active material layer 22 is a layer containing the positive electrode active material. The positive electrode active material layer 22 is stacked on the positive electrode current collector layer 21. The positive electrode active material is not particularly limited, and examples include at least one selected from the group consisting of lithium phosphate compounds with a NASICON-type structure, lithium phosphate compounds with an olivine-type structure, lithium-containing layered oxides, and lithium-containing oxides with a spinel-type structure. Examples of lithium phosphate compounds with a NASICON-type structure include Li3V2(PO4)3. Examples of lithium phosphate compounds with an olivine-type structure include Li3Fe2(PO4)3 and LiMnPO4. Examples of lithium-containing layered oxides include LiCoO2 and LiCo... 1 / 3 Ni 1 / 3 Mn 1 / 3 O2, etc. Examples of lithium-containing oxides with a spinel-type structure include LiMn2O4 and LiNi. 0.5 Mn 1.5 O4, etc.

[0022] It should be noted that the materials included in the positive electrode active material layer 22 are not limited to positive electrode active materials, but may also include solid electrolytes and sintering aids, which will be described below. Sintering aids are not particularly limited, and examples include lithium oxide, sodium oxide, potassium oxide, boron oxide, silicon oxide, bismuth oxide, and phosphorus oxide.

[0023] The negative electrode 30 has a negative electrode current collector layer 31, a negative electrode active material layer 32, and particles 33.

[0024] The negative electrode current collector layer 31 is a conductive layer. Here, in Figure 1 In this example, the -X direction end face of the negative electrode current collector layer 31 is exposed and can be connected to the outside. That is, the -X direction end face of the negative electrode current collector layer 31 becomes the negative electrode of the battery 1. The material of the negative electrode current collector layer 31 is a conductive metal, including at least one metal selected from copper, nickel, and iron. It should be noted that the material of the negative electrode current collector layer 31 is not limited to this; for example, it may also include metal materials such as palladium, gold, platinum, and aluminum. In addition, the negative electrode current collector layer 31 is not limited to being composed of a single layer; it may also be composed of multiple layers, such as stainless steel with a nickel coating on the negative electrode active material layer 32 side.

[0025] The negative electrode active material layer 32 is a layer containing the negative electrode active material. Figure 1 In this example, the negative electrode active material layer 32 is disposed in the +Z direction of the negative electrode current collector layer 31. For example... Figure 1As shown, the negative electrode active material layer 32 has a first main surface 32a and a second main surface 32b. The first main surface 32a is the main surface of the negative electrode active material layer 32 on the side opposite to the electrolyte layer 40. The second main surface 32b is the main surface of the negative electrode active material layer 32 on the side opposite to the electrolyte layer 40. Figure 1 In the example, the second main surface 32b is connected to the negative current collector layer 31.

[0026] The thickness of the negative electrode active material layer 32 is 10 μm or more. Here, the thickness of the negative electrode active material layer 32 refers to the average distance between the first main surface 32a and the second main surface 32b in the direction (Z direction) opposite to the negative electrode current collector layer 31 and the electrolyte layer 40. As a result, the energy density of the battery 1 can be improved.

[0027] The negative electrode active material layer 32 comprises at least one of tin (Sn) and silicon (Si) as the negative electrode active material. The crystallinity of silicon is not particularly limited, for example, it can be amorphous. This improves the energy density of the battery 1. In this embodiment, the negative electrode active material layer 32 comprises a negative electrode active material, and may also further comprise conductive additives and binders.

[0028] The negative electrode active material in the negative electrode active material layer 32 is continuous from the first main surface 32a to the second main surface 32b. In other words, the interior of the negative electrode active material layer 32 does not substantially contain any components of the electrolyte layer 40 (e.g., a solid electrolyte). In other words, the negative electrode active material layer 32 has a path from the main surface on the negative electrode current collector layer 31 side to the main surface on the electrolyte layer 40 side solely through the negative electrode active material. Examples of a continuous material include metal foil, wafers, etc., but it can also have a coating formed by plating, sputtering, evaporation, etc. This improves the energy density of the battery 1. Furthermore, it prevents the electron conduction path from the negative electrode current collector layer 31 to the electrolyte layer 40 from being obstructed by particles 33 formed from the insulator entering between the particles of the negative electrode active material.

[0029] It should be noted that when the negative electrode active material layer 32 contains multiple negative electrode active material particles, the particles are in direct contact with each other, so that ions or electrons are conducted through the negative electrode active material particles in a mechanism, and the first main surface 32a side and the second main surface 32b side are electrically connected through this contact. That is, multiple negative electrode active material particles are continuously formed from the first main surface 32a to the second main surface 32b.

[0030] Here, continuity means that when a straight line is drawn connecting the first principal surface 32a and the second principal surface 32b along the Z direction, there are no constituent elements (including voids) other than the active material on that line. More specifically, in at least one field of view of an observation image obtained by observing the cross-section of the negative electrode active material layer 32 using an electron microscope such as SEM, if the area of ​​the region where the straight line can be drawn is more than 50% of the total area of ​​the cross-section of the negative electrode active material layer 32, then it can be said that the negative electrode active material in the negative electrode active material layer 32 is continuous from the first principal surface 32a to the second principal surface 32b.

[0031] Particle 33 is a particle dispersed on the first principal surface 32a of the negative electrode active material layer 32. Figure 1 In this example, particle 33 is in contact with the negative electrode active material layer 32 and the electrolyte layer 40. Here, dispersion means being distributed on and disposed on a portion of the first main surface 32a. In other words, the first main surface 32a has a region in contact with the electrolyte layer 40 via particle 33, and a region in direct contact with the electrolyte layer 40. The primary particle size of particle 33 is preferably 100 nm or less. Primary particle size refers to the median particle size (D0). 50 (Particle size). Thus, particles 33 readily embed into the negative electrode current collector layer 31 and the electrolyte layer 40, and through an anchoring effect, can suppress the peeling of the negative electrode current collector layer 31 from the electrolyte layer 40. The primary particle size of particles 33 can be determined based on SEM (Scanning Electron Microscope) images or EDX (Energy Dispersive X-ray spectroscopy) mapping images.

[0032] Particle 33 possesses insulating properties. Insulating properties mean that at room temperature (above 5°C and below 35°C), its ionic conductivity is 10. -7 S / cm or less, and electronic conductivity 10 -7 The S / cm is below 1. Therefore, the contact area between the negative electrode active material layer 32 and the electrolyte layer 40 is reduced, thus suppressing the reduction and decomposition of the solid electrolyte due to side reactions during charging and discharging, and improving the discharge capacity. Furthermore, through the dielectric effect, electron conduction from the negative electrode current collector layer 31 to the electrolyte layer 40 is improved, thereby reducing the interface resistance between the negative electrode current collector layer 31 and the electrolyte layer 40, and improving the coulombic efficiency.

[0033] Particle 33 is formed of an insulator, preferably a charged insulator. A charged insulator is a material that insulates against ions and electrons. Particle 33 is an inorganic compound containing element M and oxygen (O). Element M is at least one of calcium (Ca), barium (Ba), titanium (Ti), zirconium (Zr), vanadium (V), niobium (Nb), molybdenum (Mo), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), indium (In), silicon (Si), tin (Sn), antimony (Sb), and phosphorus (P). This improves the dielectric effect, thereby further reducing the resistance at the interface between the negative electrode current collector layer 31 and the electrolyte layer 40.

[0034] The electrolyte layer 40 is disposed between the positive electrode 20 and the negative electrode 30. The electrolyte layer 40 becomes a sintered body containing a solid electrolyte. The solid electrolyte is not particularly limited as long as it is a material that allows ions to move between the positive electrode 20 and the negative electrode 30. For example, the solid electrolyte is a sulfide, such as Li6PS5Cl, Li3PS4, or Li4SnS4. By using a sulfide solid electrolyte, the thermoformability of the electrolyte layer 40 can be improved, and a good bonding interface can be formed with the positive electrode active material layer 22.

[0035] The side reinforcement 60 is provided to prevent short circuit of battery 1. Figure 1 In this example, the side reinforcement 60 is disposed on the end faces of the positive electrode 20, the negative electrode 30, and the electrolyte layer 40 in the X and Y directions. The material of the side reinforcement 60 is not particularly limited as long as it is an insulator, such as resin, glass, ceramic, etc.

[0036] It should be noted that the negative electrode and battery involved in the first embodiment are not limited to those described above. For example, when the negative electrode active material layer is a metal foil, the negative electrode may not have a negative electrode current collector layer. In this case, the negative electrode active material layer can serve as the negative electrode of the battery and be connected to the outside.

[0037] Alternatively, the battery according to the first embodiment may also be a battery with an outer packaging (shell). That is, the battery according to the first embodiment may also be a battery in which a laminate including a positive electrode 20, a negative electrode 30 and an electrolyte layer 40 is housed in an outer packaging made of metal, ceramic or the like.

[0038] As explained above, the battery 1 according to this embodiment includes: a positive electrode 20; a negative electrode 30 having a negative electrode active material layer 32 containing negative electrode active material and insulating particles 33; and an electrolyte layer 40 containing a solid electrolyte. The negative electrode active material layer 32 has a first main surface 32a located on the side of the electrolyte layer 40 and a second main surface 32b located on the side opposite to the first main surface. The negative electrode active material in the negative electrode active material layer 32 is continuous from the first main surface 32a to the second main surface 32b. The particles 33 are located on the first main surface 32a of the negative electrode active material layer 32.

[0039] As a result, the contact area between the negative electrode active material layer 32 and the electrolyte layer 40 is reduced, thus suppressing the reduction and decomposition of the solid electrolyte due to side reactions during charging and discharging, and improving the discharge capacity. In addition, through the dielectric effect, electron conduction from the negative electrode current collector layer 31 to the electrolyte layer 40 is improved, thereby reducing the resistance of the interface between the negative electrode current collector layer 31 and the electrolyte layer 40, and improving the coulombic efficiency.

[0040] As a preferred aspect, the thickness of the negative electrode active material layer 32 is 10 μm or more. This improves the energy density of the battery 1.

[0041] As a preferred aspect, the negative electrode active material includes at least one of Sn and Si. This improves the energy density of battery 1.

[0042] As a preferred aspect, particle 33 contains oxygen. This improves the dielectric effect, thereby further reducing the resistance at the interface between the negative electrode current collector layer 31 and the electrolyte layer 40, and thus further improving the coulombic efficiency.

[0043] In addition, particle 33 contains at least one of Ca, Ba, Ti, Zr, V, Nb, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Si, Sn, and Sb. In this case, the discharge capacity can also be improved.

[0044] In addition, particle 33 contains at least one of titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, indium oxide, barium titanate, and phosphorus oxide. In this case, the discharge capacity can also be improved.

[0045] As a preferred aspect, the solid electrolyte contains sulfur. This improves the thermoformability of the electrolyte layer 40 and enables it to form a good bonding interface with the positive electrode active material layer 22.

[0046] Hereinafter, an example of the method for manufacturing the negative electrode according to the first embodiment will be described. The method for synthesizing the negative electrode according to the first embodiment includes a negative electrode active material layer formation step and a particle dispersion step.

[0047] The negative electrode active material layer formation process is the process of forming the negative electrode active material layer 32. The negative electrode active material layer 32 is formed, for example, by rolling a metal foil to a thickness of 10 μm or more.

[0048] The particle dispersion process is a process of dispersing particles 33 on one main surface of the negative electrode active material layer 32. Specifically, the particles 33 are dispersed on one main surface of the negative electrode active material layer 32 by dripping a solvent containing the dispersed particles 33 onto it and allowing it to dry. Here, with the negative electrode active material layer 32 already disposed on the negative electrode current collector layer 31, the particles 33 are dispersed on the main surface of the negative electrode active material layer 32 on the side opposite to the negative electrode current collector layer 31.

[0049] It should be noted that the above-described method for manufacturing the negative electrode is only one example and is not limited to the above. For example, in the negative electrode active material layer formation process, the negative electrode active material layer 32 can also be formed by sputtering the negative electrode active material onto the negative electrode current collector layer 31 using the negative electrode active material as a vapor deposition source. In this case, in the particle dispersion process, particles 33 are dispersed on the main surface of the negative electrode active material layer 32 on the side opposite to the negative electrode current collector layer 31.

[0050] (Example)

[0051] The embodiments described below are examples of this implementation. It should be noted that this implementation is not limited to the embodiments described below.

[0052] (Example 1)

[0053] The battery described in Example 1 was fabricated using the following method. As a negative electrode active material formation step, a negative electrode active material layer was formed by rolling tin foil to a thickness of 10 μm. As a particle dispersion step, a solution was prepared by dispersing zirconium oxide (ZrO2) particles with a primary particle size of 10 nm in isopropanol at 0.1% by mass, and the solution was dispersed at a concentration of 50 μL / cm³. 2 The amount of liquid dripped onto the prepared negative electrode active material layer was air-dried and then completely dried at 100°C. Then, an electrolyte layer was prepared by pressing 150 mg of Li6PS5C powder as a solid electrolyte into granules. The prepared electrolyte layer was then adhered to the particle-containing side of the prepared particle-containing negative electrode active material layer. A counter electrode formed of In-Li alloy was adhered to the main surface of the prepared electrolyte layer on the side opposite to the negative electrode active material layer. Then, stainless steel foil was adhered to both sides as the current collector for both the negative electrode and the counter electrode, and a current collector of 1 tf / (cm²) was applied. 2 The pressure of ·min) is applied in the stacking direction to produce the battery involved in Example 1.

[0054] In the determination of charge-discharge characteristics described in Example 1, the charging capacity and coulombic efficiency were measured under the following conditions. Here, charging refers to the energy accumulation caused by lithium ions intercalating into the negative electrode, and discharging refers to the energy release caused by lithium ions deintercalating from the negative electrode.

[0055] Charging rate: 0.05C

[0056] Charging method: CCCV, 0.01C current cutoff

[0057] Charging control voltage: 5mV

[0058] Discharge rate: 0.05C

[0059] Discharge method: CC

[0060] Discharge termination voltage: 1.5V

[0061] (Example 2)

[0062] In Example 2, except that alumina (Al2O3) particles with a particle size of 20 nm were used to replace zirconium oxide (ZrO2) particles in the particle dispersion process, the battery was manufactured and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0063] (Example 3)

[0064] In Example 3, except that indium oxide (In2O3) particles with a primary particle size of 50 nm were used to replace zirconium oxide (ZrO2) particles in the particle dispersion process, the battery fabrication and charge / discharge characteristics were measured in the same manner as in Example 1.

[0065] (Example 4)

[0066] In Example 4, except that barium titanate particles (BaTiO3) with a primary particle size of 80 nm were used to replace zirconium oxide (ZrO2) particles in the particle dispersion process, the battery was fabricated and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0067] (Example 5)

[0068] In Example 5, except that Li3PS4 was used as the solid electrolyte, the battery was fabricated and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0069] (Comparative Example 1)

[0070] In Comparative Example 1, except that in the particle dispersion process, a solution prepared by dispersing Li6PS5Cl particles with a primary particle size of 100 nm in hexane at 1% by mass was used instead of a solution prepared by dispersing zirconium oxide (ZrO2) particles in isopropanol at 0.1% by mass, the battery was fabricated and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0071] (Comparative Example 2)

[0072] In Comparative Example 2, except that a solution prepared by dispersing Li3PS4 particles with a primary particle size of 100 nm in hexane at 1% by mass was used instead of a solution prepared by dispersing zirconium oxide (ZrO2) particles in isopropanol at 0.1% by mass, the battery was fabricated and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0073] Table 1 shows the measurement results of charge-discharge characteristics involved in Examples 1 to 5 and Comparative Examples 1 and 2.

[0074] [Table 1]

[0075] As shown in Table 1, in Examples 1 to 5, the discharge capacity and coulombic efficiency were improved compared with Comparative Examples 1 and 2, which used ion-conducting particles, because insulating particles were used.

[0076] (Example 6)

[0077] In Example 6, except that the thickness of the tin foil was rolled to 20 μm as part of the negative electrode active material formation process, the battery was manufactured and its charge-discharge characteristics were measured in the same manner as in Example 1.

[0078] (Comparative Example 3)

[0079] In Comparative Example 3, except that the thickness of the tin foil was rolled to 20 μm as part of the negative electrode active material formation process, the battery was manufactured and its charge-discharge characteristics were measured in the same manner as in Comparative Example 1.

[0080] Table 2 shows the measurement results of the charge-discharge characteristics involved in Example 6 and Comparative Example 3.

[0081] [Table 2]

[0082] As shown in Table 2, even when the thickness of the negative electrode active material layer is set to 20 μm, in Example 6, the discharge capacity and coulombic efficiency are improved compared to Comparative Example 3, which uses ion-conducting particles, due to the use of insulating particles.

[0083] (Example 7)

[0084] In Example 7, as the negative electrode active material layer formation process, a 12 μm thick Si film was formed by sputtering on a 20 μm thick copper foil using Si as the evaporation source, thereby fabricating the negative electrode active material layer. The sputtering was performed by magnetron sputtering using Si as the evaporation source under an argon atmosphere of 0.7 Pa. In the particle dispersion process, zirconia (ZrO2) particles with a primary particle size of 10 nm were dispersed in isopropanol at 0.1% by mass to prepare a solution, and the solution was dispersed at 50 μL / cm³. 2 The amount of material dripped onto the Si film side of the copper foil, and after air drying, it was completely dried at 100°C. Subsequent processes were performed to fabricate the battery in the same manner as in Example 1, and charge-discharge measurements were conducted under the same conditions as in Example 1.

[0085] (Example 8)

[0086] In Example 8, except that indium oxide particles with a primary particle size of 50 nm were used instead of zirconium oxide (ZrO2) particles in the particle dispersion process, the battery fabrication and charge / discharge characteristics were measured in the same manner as in Example 7.

[0087] (Comparative Example 4)

[0088] In Comparative Example 4, except that a solution prepared by dispersing Li6PS5Cl particles with a primary particle size of 100 nm in hexane at 1% by mass was used instead of a solution prepared by dispersing zirconium oxide (ZrO2) particles in isopropanol at 0.1% by mass, the battery was fabricated and its charge-discharge characteristics were measured in the same manner as in Example 7.

[0089] Table 3 shows the measurement results of charge-discharge characteristics involved in Examples 7, 8 and Comparative Example 4.

[0090] [Table 3]

[0091] As shown in Table 3, in Examples 7 and 8, when Si is used as the negative electrode active material, the discharge capacity and coulombic efficiency are improved compared to Comparative Example 4, which uses ion-conducting particles, because insulating particles are used.

[0092] The embodiments described above are for the purpose of making this disclosure easier to understand and are not intended to limit the interpretation of this disclosure. This disclosure can be modified / improved without departing from its spirit, and this disclosure also includes its equivalents.

[0093] In addition, the present invention can be adopted in the following aspects.

[0094] (1) A battery comprising: positive electrode; The negative electrode has a negative electrode active material layer containing negative electrode active material and insulating particles; and Electrolyte layer, containing solid electrolyte, The negative electrode active material layer has a first main surface located on the electrolyte layer side and a second main surface located on the side opposite to the first main surface. The negative electrode active material in the negative electrode active material layer is continuous from the first main surface to the second main surface. The particles are located on the first main surface of the negative electrode active material layer.

[0095] (2) The battery according to (1), wherein the thickness of the negative electrode active material layer is 10 μm or more.

[0096] (3) The battery according to (1) or (2), wherein the negative electrode active material comprises at least one of Sn and Si.

[0097] (4) The battery according to any one of (1) to (3), wherein the particles contain oxygen.

[0098] (5) The battery according to (4), wherein the particles comprise at least one of Ca, Ba, Ti, Zr, V, Nb, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Si, Sn, and Sb.

[0099] (6) The battery according to (4), wherein the particles comprise at least one of titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, indium oxide, barium titanate, and phosphorus oxide.

[0100] (7) The battery according to any one of (1) to (6), wherein the solid electrolyte comprises sulfur.

[0101] Explanation of reference numerals in the attached figures

[0102] 1 Battery

[0103] 10 protective layers

[0104] 20 Positive Electrode

[0105] 21 Positive current collector layer

[0106] 22 Positive electrode active material layer

[0107] 30 Negative electrode

[0108] 31 Negative current collector layer

[0109] 32 Negative electrode active material layer

[0110] 32a First Main Face

[0111] 32b Second Main Face

[0112] 33 particles

[0113] 40 Electrolyte layer

[0114] 60 Side reinforcement section.

Claims

1. A battery comprising: a positive electrode; a negative electrode having a negative electrode active material layer containing a negative electrode active material and having a particle having insulating property; and an electrolyte layer containing a solid electrolyte, the negative electrode active material layer has a first main surface on the electrolyte layer side and a second main surface on the side opposite to the first main surface, the negative electrode active material is continuous from the first main surface to the second main surface in the negative electrode active material layer, and the particle is on the first main surface of the negative electrode active material layer.

2. The battery according to claim 1, wherein a thickness of the negative electrode active material layer is 10 μm or more.

3. The battery according to claim 1 or 2, wherein the negative electrode active material contains at least one of Sn and Si.

4. The battery according to any one of claims 1 to 3, wherein the particle contains oxygen.

5. The battery according to claim 4, wherein the particle contains at least one of Ca, Ba, Ti, Zr, V, Nb, Mo, Mn, Fe, Co, Ni, Cu, Zn, Al, In, Si, Sn, Sb.

6. The battery according to claim 4, wherein the particle contains at least one of titanium oxide, zirconium oxide, aluminum oxide, zinc oxide, indium oxide, barium titanate, phosphorus oxide.

7. The battery according to any one of claims 1 to 6, wherein the solid electrolyte contains sulfur. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​

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