SOLID BATTERY ACCUMULATOR

Abstract

A solid-state accumulator according to the present embodiment comprises a positive electrode; a negative electrode; a solid electrolyte layer between the positive electrode and the negative electrode; and a first column-shaped body located at a position in the same layer as the positive electrode or the negative electrode and spaced apart from the positive electrode or the negative electrode, with a cavity enclosed between the first column-shaped body and the positive electrode or the negative electrode.

Description

TECHNICAL AREA

[0001] The present invention relates to a solid-state accumulator. Priority is claimed in Japanese patent application No. 2022-203082, filed on December 20, 2022, the contents of which are hereby incorporated by reference. BACKGROUND

[0002] In recent years, electronic technology has developed in remarkable ways. Portable electronic devices are becoming increasingly smaller, lighter, thinner, and more multifunctional. In this context, there is also a strong demand for rechargeable batteries to serve as power sources for electronic devices, making them smaller, lighter, thinner, and more reliable. Solid-state batteries, which use a solid electrolyte as their electrolyte, have attracted considerable attention.

[0003] The solid-state battery is charged and discharged by the movement of lithium ions between the positive and negative electrodes through a solid electrolyte. Patent document 1, for example, discloses a solid-state battery with a sintered solid electrolyte. Citation list patent document

[0004] [Patent Document 1] PCT International Publication No. WO2008 / 099508 SUMMARY OF THE INVENTION Technical Problem

[0005] A sintered solid-state battery can develop internal cracks due to a concentration of stresses at the interfaces of the individual layers. These cracks are associated with mismatches during sintering, volume expansion during charging and discharging, and similar factors. Internal cracking leads to a deterioration of the battery's cycle performance.

[0006] The present disclosure was made in consideration of the problems mentioned above and aims to provide a solid-state accumulator in which internal cracking is less likely to occur. Solution to the problem

[0007] To solve the problems mentioned above, the following resources will be provided. (1) A solid-state accumulator according to a first aspect comprises a positive electrode, a negative electrode, a solid electrolyte layer, and a first column-shaped body. The solid electrolyte layer is located between the positive electrode and the negative electrode. The first column-shaped body is located in the same layer as the positive electrode or the negative electrode and is spaced apart from the positive electrode or the negative electrode by a cavity enclosed between the first column-shaped body and the positive electrode or the negative electrode. (2) In the solid-state accumulator according to the above aspect, the first column-shaped body may be spaced apart from the positive electrode in the same layer as the positive electrode, enclosing the cavity between the first column-shaped body and the positive electrode. (3) The solid-state accumulator according to the above aspect may further include a second column-shaped body. The second column-shaped body is located in the same layer as the negative electrode and is spaced apart from the negative electrode, with a cavity enclosed between the second column-shaped body and the negative electrode. (4) The solid-state accumulator according to the above aspect may further include a positive electrode terminal and a negative electrode terminal. The positive electrode terminal is connected to the positive electrode on a first surface of a laminated body comprising the positive electrode, the negative electrode, and the solid electrolyte layer. The negative electrode terminal is connected to the negative electrode on a second surface of the laminated body, which is distinct from the first surface. The first column-shaped body is located between the positive electrode terminal and the negative electrode, or between the negative electrode terminal and the positive electrode. (5) In the solid-state accumulator according to the above aspect, the positive electrode terminal may be in contact with the first surface and a surface adjacent to the first surface, and the positive electrode terminal may not be in contact with the negative electrode. (6) In the solid-state accumulator according to the above aspect, the negative electrode terminal may be in contact with the second surface of the laminated body and a surface adjacent to the second surface, and the negative electrode terminal may not be in contact with the positive electrode. (7) In the solid-state accumulator according to the above aspect, the first column-shaped body can have the same layer configuration as the positive electrode or the negative electrode. (8) In the solid-state accumulator according to the above aspect, the thickness of the positive electrode may be 2.5 times or more in relation to the thickness of the solid electrolyte layer. (9) In the solid-state accumulator according to the above aspect, the thickness of the negative electrode may be 2.5 times or more in relation to the thickness of the solid electrolyte layer. (10) In the solid-state accumulator according to the above aspect, the positive electrode may have a thickness of 10 µm or more. (11) In the solid-state accumulator according to the above aspect, the negative electrode may have a thickness of 10 µm or more. (12) In the solid-state accumulator according to the above aspect, the positive electrode can be at least one layer, the negative electrode can be at least one layer, and The total number of positive and negative electrodes can be 3 or more. (13) In the solid-state accumulator according to the above aspect, a laminated body comprising the positive electrode, the negative electrode, and the solid electrolyte layer may have a first positive electrode and a second positive electrode adjacent to each other in a lamination direction. A first cavity located between the first positive electrode and the column-shaped body in the same layer as the first positive electrode, and a second cavity located between the second positive electrode and the column-shaped body in the same layer as the second positive electrode, overlap at least partially when viewed from the lamination direction of the laminated body. (14) In the solid-state accumulator according to the above aspect, 80% or more of the first cavity may overlap with the second cavity when viewed from the lamination direction of the laminated body. (15) In the solid-state accumulator according to the above aspect, a laminated body comprising the positive electrode, the negative electrode, and the solid electrolyte layer may have a first negative electrode and a second negative electrode adjacent to each other in a lamination direction. A third cavity located between the first negative electrode and the column-shaped body in the same layer as the first negative electrode, and a fourth cavity located between the second negative electrode and the column-shaped body in the same layer as the second negative electrode, overlap at least partially when viewed from the lamination direction of the laminated body. (16) In the solid-state accumulator according to the above aspect, 80% or more of the third cavity may overlap with the fourth cavity when viewed from the lamination direction of the laminated body. (17) The solid-state accumulator according to the above aspect may further include a first area containing a solid electrolyte which forms the solid electrolyte layer between the positive electrode or the negative electrode and the first column-shaped body, in the same layer as that of the positive electrode or the negative electrode. (18) The solid-state accumulator according to the above aspect may further include a third column-shaped body between the positive electrode or the negative electrode and the first column-shaped body in the same layer as that of the positive electrode or the negative electrode. (19) The solid-state accumulator according to the above aspect may have a portion of the first column-shaped body or a fourth column-shaped body at a position in the second direction of the positive electrode or the negative electrode. Here, a direction from the first column-shaped body to the positive electrode or the negative electrode in the same layer as that of the positive electrode or the negative electrode is defined as a first direction, including the cavity between the first column-shaped body and the positive electrode or the negative electrode, and a direction intersecting the first direction is defined as a second direction. (20) In the solid-state accumulator according to the aspect above, the width of the cavity in the first direction may be 0.07 times or more, or 15.0 times or less, with respect to the width of the first column-shaped body in the first direction. Here, a direction from the first column-shaped body to the positive electrode or the negative electrode in the same layer as the positive electrode or the negative electrode is defined as a first direction, including the cavity between the first column-shaped body and the positive electrode or the negative electrode. Advantageous effects of the invention

[0008] In a solid-state accumulator, the occurrence of internal cracks is less likely according to the above aspect. BRIEF DESCRIPTION OF THE DRAWINGS Fig. Figure 1 is a cross-sectional view of a solid-state accumulator according to a first embodiment. Fig. Figure 2 is a cross-sectional view obtained by cutting the solid-state accumulator according to the first embodiment along the positive electrode. Fig. Figure 3 is a cross-sectional view obtained by cutting the solid-state accumulator according to the first embodiment along the negative electrode. Fig. Figure 4 is a cross-sectional view of a characteristic part of the solid-state accumulator according to the first embodiment. Fig. Figure 5 is a cross-sectional view of a characteristic part of a solid-state accumulator according to a first modification example. Fig. Figure 6 is a cross-sectional view of a characteristic part of a solid-state accumulator according to a second modification example. Fig. Figure 7 is a cross-sectional view of a characteristic part of a solid-state accumulator according to a third modification example. Fig. Figure 8 is a cross-sectional view of a characteristic part of a solid-state accumulator according to a fourth modification example. Fig. Figure 9 is a cross-sectional view of a characteristic part of a solid-state accumulator according to a fifth modification example. Fig. Figure 10 is a cross-sectional view obtained by cutting a solid-state accumulator along the positive electrode according to a sixth modification example. Fig. Figure 11 is a cross-sectional view obtained by cutting a solid-state accumulator along the negative electrode according to a sixth modification example. Fig. Figure 12 is a cross-sectional view of a characteristic part of the solid-state accumulator according to the sixth modification example. Fig.Figure 13 is a cross-sectional view of a characteristic part of the solid-state accumulator according to the sixth modification example. DESCRIPTION OF THE EXECUTION FORMS

[0009] The present embodiments are described in detail below with reference to the drawings. The drawings used in the following description may show characteristic parts on an enlarged scale to facilitate understanding of the features of the present invention, and therefore the dimensional ratios or the like of the respective constituent elements may differ from the actual ones. The materials, dimensions, and the like shown by way of example in the following description are merely examples, and the present invention is not limited to them. Therefore, a suitable modification can be made within the scope of the present invention that does not deviate from the core of the present invention.

[0010] The directions are defined. A lamination direction of a laminated body 10 is called the z-direction, a direction in a plane orthogonal to the z-direction is called the x-direction, and a direction orthogonal to both the x-direction and the z-direction is called the y-direction. The x-direction is, for example, a direction from a positive electrode terminal 80 to a negative electrode terminal 90. For example, a direction from a columnar body 4 to a positive electrode 1 in the same layer as the positive electrode 1, and a direction from a columnar body 6 to a negative electrode 2 in the same layer as the negative electrode 2, are both examples of the x-direction. The x-direction is an example of a first direction. Furthermore, the y-direction is an example of a second direction.In the following, a direction in the z-direction can be described as "upwards" and a direction opposite to this as "downwards". Up and down do not necessarily correspond to the direction of gravity.

[0011] Fig. Figure 1 is a cross-sectional view of a solid-state accumulator 100 according to a first embodiment. Fig. Figure 2 is a cross-sectional view obtained by cutting the solid-state accumulator 100 according to the first embodiment along the positive electrode 1. Fig. Figure 3 is a cross-sectional view obtained by cutting the solid-state accumulator 100 according to the first embodiment along the negative electrode 2. Fig. Figure 4 is a cross-sectional view of a characteristic part of the laminated body 10 of the solid-state accumulator 100 according to the first embodiment.

[0012] The solid-state battery 100, for example, has the laminated body 10, the positive electrode terminal 80, and the negative electrode terminal 90. The solid-state battery 100 is, for example, a laminate battery, a square-type battery, a cylindrical-type battery, a coin-type battery, and a button-type battery. The solid-state battery 100 can be a liquid-injection type, obtained by dissolving or dispersing a solid electrolyte layer 3 in a solvent. <Laminierter Körper>

[0013] The laminated body 10 comprises the positive electrode 1, the negative electrode 2, the solid electrolyte layer 3, the columnar body 4, and the columnar body 6. The columnar body 4 is located in the same layer as the positive electrode 1. A cavity 5 is located between the positive electrode 1 and the columnar body 4. The columnar body 6 is located in the same layer as the negative electrode 2. A cavity 7 is located between the negative electrode 2 and the columnar body 6. The columnar body 4 is an example of a first columnar body. The columnar body 6 is an example of a second columnar body.

[0014] The laminated body 10 is charged or discharged by the exchange of ions between the positive electrode 1 and the negative electrode 2 through the solid electrolyte layer 3. The laminated body 10 can, for example, be a laminated body in which the positive electrode 1, the negative electrode 2, and the solid electrolyte layer 3 are laminated together. The laminated body 10 can also be a wound body obtained by winding a laminated body in which the positive electrode 1, the negative electrode 2, and the solid electrolyte layer 3 are laminated together. "Positive electrode"

[0015] The number of layers of the positive electrode 1 in the laminated body 10 is irrelevant. The positive electrode 1 can be present once or multiple times. Each positive electrode 1 extends in the xy-plane. A first end of each positive electrode 1 is connected to the electrode terminal 80 on a first surface S1 of the laminated body 10. The second end of each positive electrode 1 is exposed to the cavity 5. The second end of each positive electrode 1 faces the columnar body 4, with the cavity 5 enclosed between the second end and the cavity 5.

[0016] The thickness of the positive electrode 1 is, for example, 2.5 times or more than the thickness of the solid electrolyte layer 3. The thickness of the positive electrode 1 is, for example, 10 µm or more.

[0017] As in Fig.As shown in Figure 4, the positive electrode 1, for example, has a positive electrode current collector layer 11 and a positive electrode active material layer 12.

[0018] The positive electrode current collector layer 11 contains, for example, a highly conductive material. The positive electrode current collector layer 11 is, for example, a metal or an alloy containing at least one metallic element from the group consisting of silver (Ag), palladium (Pd), gold (Au), platinum (Pt), aluminum (Al), copper (Cu), and nickel (Ni). Furthermore, the positive electrode current collector layer 11 can also be formed from a non-metal, such as carbon (C), as long as it is conductive. The positive electrode current collector layer 11 is, for example, formed from Ag or an AgPd alloy.

[0019] The positive electrode active material layer 12 is formed on one or both surfaces of the positive electrode current collector layer 11. The positive electrode active material layer 12 contains a positive electrode active material. The positive electrode active material layer 12 may contain a conductive additive, a binder, and a solid electrolyte, which are described below.

[0020] The positive electrode active material is, for example, a transition metal oxide or a mixed transition metal oxide. Specific examples of positive electrode active materials are lithium manganese compound oxide (Li₂Mn₂). a Ma 1-a O3 (0.8 ≤ a ≤ 1, Ma = Co, Ni), lithium cobaltate (LiCoO2), lithium nickelate (LiNiO2), lithium manganate with spinel structure (LiMn2O4), a composite metal oxide of the general formula: LiNi x Co y Mn zO2 (x + y + z = 1, 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, 0 ≤ z ≤ 1), a lithium-vanadium compound (LiV2O5), olivine of the type LiMbPO4 (here Mb represents one or more types of elements, selected from Co, Ni, Mn, Fe, Mg, Nb, Ti, Al and Zr), lithium vanadium phosphate (Li3V2(PO4)3 or LiVOPO4), a positive electrode based on a lithium excess mixed crystal, represented by Li2MnO3-LiMcO2 (Mc = Mn, Co, Ni), lithium titanate (Li4Ti5O 12 ), titanium oxide (TiO2) and a composite metal oxide, represented by Li s Ni t Co u Al v O2 (0.9 < s < 1.3, 0.9 < t + u + v < 1.1).

[0021] Furthermore, part of each element from which these positive electrode active materials are formed can be replaced by a heteroelement, and the composition ratio of these positive electrode active materials can deviate from the stoichiometric composition.

[0022] The conductive auxiliary is not particularly limited as long as it improves the electronic conductivity in the positive electrode active material layer 12, and any commonly known conductive auxiliary can be used. Examples of conductive auxiliary materials include a carbon-based material such as graphite, carbon black, graphene, or a carbon nanotube; a metal such as gold, platinum, silver, palladium, aluminum, copper, nickel, stainless steel, or iron; a conductive oxide such as ITO; and a mixture thereof. The conductive auxiliary can be in the form of either a powder or fibers.

[0023] The binding material connects the positive electrode current collector layer 11 and the positive electrode active material layer 12, connects the positive electrode active material layer 12 and the solid electrolyte layer 3, and connects the different materials from which the positive electrode active material layer 12 is formed.

[0024] The binder can be used in a range that does not impair the function of the positive electrode active material layer 12. If a binder is not required, it can be omitted from the positive electrode active material layer 12. The binder content in the positive electrode active material layer 12 is, for example, 0.5 volume percent or more and 30 volume percent or less. If the proportion of the binder is sufficiently low, the resistance of the positive electrode active material layer 12 will be sufficiently low. The volume fraction (vol%) is, for example, essentially equal to an area fraction in a cross-section measured with a scanning electron microscope. The area ratio in a cross-section measured with a scanning electron microscope can be considered, as it is, the volume ratio.

[0025] The binding material can be any material capable of performing the bonding described above. For example, a fluorinated resin such as polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (PTFE) is an example of a binding material. Furthermore, the binding material can be, for example, cellulose, styrene-butadiene rubber, ethylene-propylene rubber, a polyimide resin, or a polyamide-imide resin. Additionally, the binding material can also be a conductive polymer with electronic conductivity or an ionically conductive polymer with ionic conductivity. An example of a conductive polymer with electronic conductivity is polyacetylene.The ion-conducting polymer with ion conductivity is, for example, a compound ion-conducting polymer formed from a monomer of a polymer compound (a polyether-based polymer compound such as polyethylene oxide or polypropylene oxide or polyphosphazene) and a lithium salt such as LiClO4, LiBF4, and LiPF6 or an alkali metal salt consisting mainly of lithium.

[0026] Fig. Figure 4 shows an example in which the positive electrode 1 consists of the positive electrode current collector layer 11 and the positive electrode active material layer 12; however, the positive electrode 1 is not limited to this case. For example, the positive electrode 1 can be a single layer in which a positive electrode current collector and a positive electrode active material are combined. "Negative electrode"

[0027] The number of layers of the negative electrode 2 in the laminated body 10 is irrelevant. The negative electrode 2 can be present once or multiple times. For example, the total number of layers of the positive electrode 1 and the layers of the negative electrode 2 in the laminated body 10 is three or more.

[0028] Each negative electrode 2 extends in the xy-plane. The first end of each negative electrode 2 is connected to the negative electrode terminal 90 on the second surface S2 of the laminated body 10. The first surface S1 and the second surface S2 are distinct surfaces of the laminated body 10. For example, the first surface S1 and the second surface S2 are opposite each other. The second end of each negative electrode 2 is exposed to the cavity 7. The second end of each negative electrode 2 faces the columnar body 6, with the cavity 7 enclosed between the second end and the columnar body 6.

[0029] The thickness of the negative electrode 2 is, for example, 2.5 times or more in relation to the thickness of the solid electrolyte layer 3. The thickness of the negative electrode 2 is, for example, 10 µm or more.

[0030] As in Fig.As shown in Figure 4, the negative electrode 2, for example, has a negative electrode current collector layer 21 and a negative electrode active material layer 22.

[0031] The negative electrode current collector layer 21 contains, for example, a highly conductive material. The same material as the material of the positive electrode current collector layer 11 can be used for the negative electrode current collector layer 21. The negative electrode current collector layer 21 is, for example, made of Ag or an AgPd alloy.

[0032] The negative electrode active material layer 22 is formed on one or both surfaces of the negative electrode current collector layer 21. The negative electrode active material layer 22 contains a negative electrode active material. The negative electrode active material layer 22 may contain a conductive additive, a binder, and a solid electrolyte, which are described below.

[0033] The negative electrode active material is a compound that can absorb and release ions. It has a lower potential than the positive electrode active material. The same material used for the positive electrode active material can be used for the negative electrode active material. The negative and positive electrode active materials used in the solid-state battery 100 are selected based on their respective potentials. For example, the negative electrode active material includes Li4TisO. 12 , LiTiO2, Li2TiO3, Li2TiSiO5, and a mixture thereof.

[0034] The conductive auxiliary improves the electronic conductivity of the negative electrode active material layer 22. The same material can be used for the conductive auxiliary as for the positive electrode active material layer 12.

[0035] The binder material connects the negative electrode current collector layer 21 and the negative electrode active material layer 22, connects the negative electrode active material layer 22 and the solid electrolyte layer 3, and connects the various materials from which the negative electrode active material layer 22 is formed. The same material as the material of the positive electrode active material layer 12 can be used for the binder material. The proportion of the binder material can be the same as the proportion of the positive electrode active material layer 12. If a binder material is not required, it can be omitted from the negative electrode current collector layer 21.

[0036] Fig.Figure 4 shows an example in which the negative electrode 2 consists of the negative electrode current collector layer 21 and the negative electrode active material layer 22; however, the negative electrode 2 is not limited to this case. For example, the negative electrode 2 can be a single layer in which a negative electrode current collector and a negative electrode active material are combined. "Solid electrolyte layer"

[0037] The solid electrolyte layer 3 is located between the positive electrode 1 and the negative electrode 2. The solid electrolyte layer 3 contains a solid electrolyte. The solid electrolyte is a substance that can move ions when subjected to an externally applied electric field. The solid electrolyte layer 3 conducts, for example, lithium ions and inhibits the movement of electrons. The solid electrolyte layer 3 is, for example, a sintered body produced by sintering.

[0038] For the solid electrolyte layer 3, a substance with low electronic conductivity and high lithium-ion conductivity is preferably used. The solid electrolyte layer 3 includes, for example, a perovskite-type compound such as La 0,5 Li 0,5 TiO3, a LISICON-type compound like Li 14 Zn(GeO4)4, a garnet-type compound like Li7La3Zr2O 12 , a NASICON-type compound such as LiZr2(PO4)3, Li 1,3 Al 0,3 Ti 1,7 (PO4)3, Li 1,5 Al 0,5 Ge 1,5 (PO4)3 ,a thio-LISICON type compound like Li 3,25 Ge 0,25 P 0.75 S4, or Li3PS4, a glass compound such as Li2S-P2S5 or Li2O-V2O5-SiO2, and a phosphate compound such as Li3PO4, Li3,5Si 0,5 P 0,5 O4, or Li 2,9 PO 3,3 N 0,46 .

[0039] Solid electrolyte layer 3, for example, contains a solid electrolyte with a γ-Li3PO4 crystal structure. This solid electrolyte has excellent ionic conductivity. Examples of solid electrolytes include Li 3+x Si x P 1-x O4, Li 3+x Si x V 1-x O4, Li 3+x Ge x P 1-x O4, and Li 3+x Ge x V 1-x O4, where Li 3+x Si x P 1-x O4 is preferable. x satisfies 0.4 ≤ x ≤ 0.8. Furthermore, the solid electrolyte can also be a ternary lithium oxide containing Si, V and Ge. “Column-shaped body”

[0040] The column-shaped body 4 is located in the same layer as the positive electrode 1. The column-shaped body 4 is an example of a first column-shaped body. The column-shaped body 4 is located at a position spaced from the positive electrode 1, with the cavity 5 enclosed between the column-shaped body 4 and the positive electrode 1. The column-shaped body 4 is located at a position offset from the positive electrode 1 in the x-direction, with the cavity 5 enclosed between the column-shaped body 4 and the positive electrode 1. The column-shaped body 4 extends in the xy-plane. The column-shaped body 4 is located between the positive electrode 1 and the negative electrode terminal 90 in the x-direction. A first lateral surface of the column-shaped body 4 in the x-direction is exposed to the cavity 5.A second lateral surface of the column-shaped body 4 in the x-direction is in contact with, for example, the negative electrode terminal 90. This second lateral surface of the column-shaped body 4 in the x-direction can, for example, be spaced away from the negative electrode terminal 90. A cavity can be present between the column-shaped body 4 and the negative electrode terminal 90.

[0041] A third lateral surface of the columnar body 4 in the y-direction is, for example, exposed at the third surface S3 of the laminated body 10, and a fourth lateral surface of the columnar body 4 in the y-direction is, for example, exposed at the fourth surface of the laminated body 10. The columnar body 4 extends, for example, in the y-direction from the third surface S3 to the fourth surface S4 of the laminated body 10. The columnar body 4 carries the solid electrolyte layers 3, which are located above the positive electrode 1.

[0042] As in Fig.As shown in Figure 4, the column-shaped body 4 has, for example, a first layer 41 and a second layer 42. The second layer 42 is formed on one or both surfaces of the first layer 41. The second layer 42 encloses, for example, the first layer 41 in the z-direction. The first layer 41 is formed, for example, from the same material as the material of the positive electrode current collector layer 11. The second layer 42 is formed, for example, from the same material as the material of the positive electrode active material layer 12. The column-shaped body 4 has, for example, the same layer configuration as the positive electrode 1. The second layer 42 is formed, for example, from the same material and has the same thickness as the positive electrode active material layer 12. The first layer 41 is formed, for example, from the same material and has the same thickness as the positive electrode current collector layer 11.

[0043] The thickness of the columnar body 4 is, for example, 2.5 times or more than the thickness of the solid electrolyte layer 3. The thickness of the columnar body 4 is, for example, 10 µm or more.

[0044] The cavity 5 is located between the positive electrode 1 and the column-shaped body 4 in the same layer as the positive electrode 1. For example, the cavity 5 is exposed on both the third surface S3 and the fourth surface S4 of the laminated body 10 and extends from the third surface S3 to the fourth surface S4. The interior of the cavity 5 can be vacuum-sealed, filled with a gas, or filled with a liquid.

[0045] The cavities 5 adjacent in the z-direction overlap, for example, at least partially when viewed in the z-direction. For example, the first cavity 5A and the second cavity 5B overlap at least partially when viewed from the z-direction. For example, the first cavity 5A overlaps the second cavity 5B by 80% or more when viewed in the z-direction. The first cavity 5A is a cavity 5 located in the same layer as the first positive electrode 1A. The first positive electrode 1A is one of the positive electrodes 1 in the laminated body 10. The second cavity 5B is a cavity 5 located in the same layer as the second positive electrode 1B. The second positive electrode 1B is a positive electrode 1 in the laminated body 10 that borders the first positive electrode 1A in the z-direction.

[0046] Furthermore, in a case where the number of positive electrodes 1 is three or more, each of the cavities 5 that lie in the same plane as each of the positive electrodes 1 can, when viewed in the z-direction, overlap at least partially with all other cavities 5. Moreover, for example, 80% or more of the first cavity 5A can overlap with all other cavities 5 when viewed in the z-direction.

[0047] The column-shaped body 6 is located in the same layer as the negative electrode 2. The column-shaped body 6 is an example of a second column-shaped body. The column-shaped body 6 is located at a position spaced from the negative electrode 2, with the cavity 7 enclosed between the column-shaped body 6 and the negative electrode 2. The column-shaped body 6 is located at a position offset in the x-direction from the negative electrode 2, with the cavity 7 enclosed between the column-shaped body 6 and the negative electrode 2. The column-shaped body 6 extends in the xy-plane. The column-shaped body 6 is located between the negative electrode 2 and the positive electrode terminal 80 in the x-direction. A first lateral surface of the column-shaped body 6 in the x-direction is exposed to the cavity 7.A second lateral surface of the column-shaped body 6 in the x-direction is, for example, in contact with the positive electrode terminal 80. This second lateral surface of the column-shaped body 6 in the x-direction can, for example, be spaced away from the positive electrode terminal 80. A cavity can be present between the column-shaped body 6 and the positive electrode terminal 80.

[0048] A third lateral surface of the columnar body 6 in the y-direction is, for example, exposed at the third surface S3 of the laminated body 10, and a fourth lateral surface of the columnar body 6 in the y-direction is, for example, exposed at the fourth surface of the laminated body 10. The columnar body 6 extends, for example, in the y-direction from the third surface S3 to the fourth surface S4 of the laminated body 10. The columnar body 6 carries the solid electrolyte layers 3, which are located above the negative electrode 2.

[0049] As in Fig.As shown in Figure 4, the column-shaped body 6 has, for example, a first layer 61 and a second layer 62. The second layer 62 is formed on one or both surfaces of the first layer 61. The second layers 62 enclose, for example, the first layer 61 in the z-direction. The first layer 61 is, for example, made of the same material as the material of the negative electrode current collector layer 21. The second layer 62 is, for example, made of the same material as the material of the negative electrode active material layer 22. The column-shaped body 6 has, for example, the same layer configuration as the negative electrode 2. The second layer 62 is, for example, made of the same material and has the same thickness as the negative electrode active material layer 22. The first layer 61 is, for example, made of the same material and has the same thickness as the negative electrode current collector layer 21.

[0050] The thickness of the columnar body 6 is, for example, 2.5 times or more than the thickness of the solid electrolyte layer 3. The thickness of the columnar body 6 is, for example, 10 µm or more.

[0051] The cavity 7 is located between the negative electrode 2 and the column-shaped body 6 in the same layer as the negative electrode 2. For example, the cavity 7 is exposed on both the third surface S3 and the fourth surface S4 of the laminated body 10 and extends from the third surface S3 to the fourth surface S4. The interior of the cavity 7 can be vacuum-sealed, filled with a gas, or filled with a liquid.

[0052] The cavities 7 adjacent in the z-direction overlap, for example, at least partially when viewed in the z-direction. For example, the first cavity 7A and the second cavity 7B overlap at least partially when viewed in the z-direction. For example, the first cavity 7A and the second cavity 7B overlap by 80% or more when viewed from the z-direction. The first cavity 7A is a cavity 7 located in the same layer as the first negative electrode 2A. The first negative electrode 2A is one of the negative electrodes 2 in the laminated body 10. The second cavity 7B is a cavity 7 located in the same layer as the second negative electrode 2B. The second negative electrode 2B is the negative electrode 2 of the laminated body 10 that borders the first negative electrode 2A in the z-direction.

[0053] Furthermore, in a case where the number of negative electrodes 2 is three or more, each of the cavities 7 that are in the same plane as each of the negative electrodes 2 can overlap at least partially with all other cavities 7 when viewed in the z-direction. Moreover, for example, 80% or more of the first cavity 7A can overlap with all other cavities 7 when viewed in the z-direction. <Positiver Elektrodenanschluss>

[0054] The electrode terminal 80 is in contact with the first surface S1 of the laminated body 10. The positive electrode terminal 80 covers the first surface S1 of the laminated body 10. A portion of the positive electrode terminal 80 may extend to a surface adjacent to the first surface S1. The electrode terminal 80 may be in contact with the first surface S1 and the surfaces adjacent to the first surface (the third and fourth surfaces). For example, the positive electrode terminal 80 may cover a portion of the third surface S3 of the laminated body 10 and a portion of the fourth surface S4 of the laminated body 10. The positive electrode terminal 80 covering the third surface S3 and the fourth surface S4 is not in contact with either of the negative electrodes 2. The positive electrode terminal 80 contains a conductive material.The electrode connection 80 can, for example, contain the same material as the material of the positive electrode current collector layer 11. The electrode connection 80 serves to establish an electrical connection between the laminated body 10 and an external pad. <Negativer Elektrodenanschluss>

[0055] The negative electrode terminal 90 is in contact with the second surface S2 of the laminated body 10. The negative electrode terminal 90 covers the second surface S2 of the laminated body 10. A portion of the negative electrode terminal 90 may extend to a surface adjacent to the second surface S2. The negative electrode terminal 90 may be in contact with the second surface S2 and the surfaces adjacent to the second surface (the third and fourth surfaces). For example, the negative electrode terminal 90 may cover a portion of the third surface S3 of the laminated body 10 and a portion of the fourth surface S4 of the laminated body 10. The negative electrode terminal 90 covering the third surface S3 and the fourth surface S4 is not in contact with any of the positive electrodes 1. The negative electrode terminal 90 contains a conductive material.The negative electrode terminal 90 can, for example, contain the same material as the material of the negative electrode current collector layer 21. The electrode terminal 90 serves to establish an electrical connection between the laminated body 10 and an external pad. “Manufacturing process for solid-state accumulators”

[0056] A manufacturing process for the solid-state accumulator 100 is described. First, the laminated body 10 is produced. The laminated body 10 is produced, for example, by a simultaneous sintering process or a sequential sintering process.

[0057] Simultaneous sintering is a process in which the materials are laminated to form the individual layers and then sintered together at once to produce the laminated body 10. Sequential sintering is a process in which sintering is performed after each layer has been formed. Simultaneous sintering allows the laminated body 10 to be produced with fewer steps than sequential sintering. Furthermore, the laminated body 10 produced by simultaneous sintering is denser than the laminated body 10 produced by sequential sintering. An example applying the simultaneous sintering process is described below.

[0058] First, the materials for the positive electrode current collector layer 11, the positive electrode active material layer 12, the solid electrolyte layer 3, the negative electrode active material layer 22, and the negative electrode current collector layer 21, which form the laminated body 10, are processed into a paste. The method for preparing each material into a paste is not particularly restricted, and, for example, a method is used in which a powder of each material is mixed with a carrier to obtain a paste. The vehicle is a general term here for a medium in the liquid phase. The vehicle contains a solvent and a binder.

[0059] A green film is then produced. This is achieved by applying a paste specifically formulated for each material to a carrier material such as PET (polyethylene terephthalate) film, allowing it to dry if necessary, and then peeling off the carrier material. The coating method for the paste is not particularly limited, and a commonly used method such as screen printing, coating, transfer, or doctor blade application can be employed.

[0060] The first layer 41 of the columnar body 4 can be formed simultaneously with the coating of the positive electrode current collector layer 11. The second layer 42 of the columnar body 4 can be formed simultaneously with the coating of the positive electrode active material layer 12. When a portion serving as a cavity 5 is masked and then the paste for the positive electrode 1 is applied, the columnar body 4 is formed. Furthermore, the area serving as a cavity 5 can be filled with a sacrificial material that sublimates upon heating. When the laminated body is sintered, the sacrificial material sublimates, and the cavity 5 is formed. The sacrificial material can, for example, be the same material as the binder.

[0061] The first layer 61 of the columnar body 6 can be formed simultaneously with the coating of the negative electrode current collector layer 21. The second layer 62 of the columnar body 6 is formed simultaneously with the coating of the negative electrode active material layer 22. The columnar body 6 is formed when a portion serving as a cavity 7 is masked and then the paste for the negative electrode 2 is applied. Alternatively, the area serving as a cavity 7 can be filled with a sacrificial material that sublimates upon heating. When the laminated body is sintered, the sacrificial material sublimates, and the cavity 7 is formed. The sacrificial material can, for example, be the same material as the binder.

[0062] The green film prepared for each material is then stacked in the desired sequence and with the required number of layers to produce a laminated film. During the lamination process, the green films are aligned and cut as needed. For example, when manufacturing a parallel or series-parallel accumulator, the orientation is adjusted so that the end surfaces of the positive electrode current collector layer 11 and the negative electrode current collector layer 21 do not coincide, and each green film is stacked accordingly.

[0063] The laminated film can be produced by a process for manufacturing a positive electrode assembly and a negative electrode assembly and laminating these assemblies. The positive electrode assembly is a laminated film in which the solid electrolyte layer 3, the positive electrode active material layer 12, the positive electrode current collector layer 11, and the positive electrode active material layer 12 are laminated in that order. The first layer 41 is formed in the same plane as the positive electrode current collector layer 11, and the second layer 42 is formed in the same plane as the positive electrode active material layer 12. The negative electrode assembly is a laminated film in which the solid electrolyte layer 3, the negative electrode active material layer 22, the negative electrode current collector layer 21, and the negative electrode active material layer 22 are laminated in that order.The first layer 61 is formed in the same plane as the negative electrode current collector layer 21, and the second layer 62 is formed in the same plane as the negative electrode active material layer 22. The lamination is carried out such that the solid electrolyte layer 3 of the positive electrode unit and the negative electrode active material layer 22 of the negative electrode unit are opposite each other, or that the positive electrode active material layer 12 of the positive electrode unit and the solid electrolyte layer 3 of the negative electrode unit are opposite each other.

[0064] The laminated film is then subjected to a common pressure application to increase the adhesion between the layers. This pressure application can be carried out, for example, by a die press, a hot isostatic press (WIP), a cold isostatic press (CIP), an isostatic press, or similar equipment. The pressure application is preferably performed with simultaneous heating. The heating temperature during the press bonding process is, for example, 40°C to 95°C. Next, after pressure application, the laminated body is cut into chips using a cutting device. The chips then undergo a debinding treatment and sintering to obtain a laminated body 10 consisting of a sintered body.

[0065] The binder removal treatment is performed in a separate step from the sintering step. By performing the binder removal step, the binder component contained in the chips is decomposed by heating before the sintering step, thus preventing rapid decomposition of the binder component during sintering. In the binder removal step, the laminated body is heated, for example, in an air atmosphere at a temperature of 300°C or higher and 800°C or lower for a period of 0.1 hours or more and 10 hours or less. The atmosphere in the binder removal step is an oxygen partial pressure environment in which the materials comprising the positive electrode, the negative electrode, and the solid electrolyte experience little or no oxidation and reduction.The type of gas used in the binder removal step can be chosen arbitrarily, provided that the materials comprising the positive electrode, the negative electrode, and the solid electrolyte do not react with the atmospheric gas. For example, the binder removal step can be carried out in a nitrogen atmosphere, an argon atmosphere, a nitrogen-hydrogen mixture, a water vapor atmosphere, or an atmosphere obtained by mixing these.

[0066] The sintering step is performed, for example, by placing the chip onto a ceramic substrate. Sintering is carried out, for example, by heating the laminated body to 600°C to 1000°C in a nitrogen atmosphere. The sintering time is set, for example, to 0, 1, or 3 hours. The atmosphere during the sintering step is an environment with a partial pressure of oxygen, in which the materials comprising the positive electrode, the negative electrode, and the solid electrolyte are not, or only minimally, oxidized and reduced. The type of gas used in the sintering step can be chosen arbitrarily, ensuring that the materials forming the positive electrode, the negative electrode, and the solid electrolyte do not react with the atmospheric gas.For example, the sintering step can be carried out in a nitrogen atmosphere, an argon atmosphere, a nitrogen-hydrogen mixed atmosphere, a water vapor atmosphere, or an atmosphere obtained by mixing these atmospheres.

[0067] Furthermore, the sintered laminated body 10 can be placed in a cylindrical container along with a polishing material such as aluminum oxide and subjected to drum polishing. This allows the edges of the laminated body 10 to be chamfered. Polishing can also be carried out using sandblasting. Sandblasting is preferable because it allows for the removal of only specific areas.

[0068] The positive electrode terminal 80 is formed on the first surface S1 of the manufactured laminated body 10, and the negative electrode terminal 90 is formed on the second surface S2. The positive electrode terminal 80 and the negative electrode terminal 90 can be produced using methods such as sputtering, dipping, screen printing, or spray coating. The solid-state accumulator 100 can be manufactured by such steps as described above. In a case where the positive electrode terminal 80 and the negative electrode terminal 90 are formed only on predetermined sections, masking with adhesive tape or similar material is carried out, and then the treatment described above is performed.

[0069] The solid-state accumulator 100 according to the present embodiment has the column-shaped body 4 and the column-shaped body 6. The column-shaped body 4 and the column-shaped body 6 support the solid electrolyte layers 3 adjacent to the column-shaped body 4 or the column-shaped body 6. The column-shaped body 4 and the column-shaped body 6 can suppress the concentration of stresses in the solid electrolyte layer 3 during pressurization and sintering during manufacturing. If the solid-state accumulator 100 further comprises the cavity 5 and the cavity 7, the cavity 5 and the cavity 7 also reduce the stress exerted on the interior of the solid-state accumulator 100.Therefore, even in a case where the positive electrode active material layer 12 and the negative electrode active material layer 22 undergo a change in volume during the charging and discharging of the solid-state accumulator 100, and then a deformation occurs inside the solid-state accumulator 100, it is possible to suppress the occurrence of cracks inside the solid-state accumulator 100.

[0070] As described above, the embodiments of the present invention have been described in detail with reference to the drawings. However, each of the configurations and the combination thereof in each embodiment are examples, and additions, omissions, substitutions and other changes to the configuration can be made without departing from the spirit of the present invention.

[0071] Fig.Figure 5, for example, is a cross-sectional view of a laminated body 10A of a solid-state accumulator according to a first modification example. The laminated body 10A differs from the laminated body 10 in the configurations of the columnar body 4 and the columnar body 6. The columnar body 4 and the columnar body 6 in the laminated body 10A consist of a single layer. Although in Fig.As shown in Figure 5, where both columnar body 4 and columnar body 6 consist of a single layer, it is also possible for only one of the two columnar bodies 4 and 6 to consist of a single layer. Even if columnar body 4 or columnar body 6 is a single layer, it can support the adjacent solid electrolyte layers 3, thus achieving the same effect as in the laminated body 10. The materials of which the single-layer columnar body 4 and the single-layer columnar body 6 are made are not of particular importance. For example, the single-layer columnar body 4 and the single-layer columnar body 6 contain the same material as the material of the solid electrolyte from which the solid electrolyte layer 3 is formed.

[0072] Furthermore, Fig.Figure 6 shows a cross-sectional view of a laminated body 10B of a solid-state accumulator according to a second modification example. The laminated body 10B differs from the laminated body 10 in that the columnar body 6 and the cavity 7 are not present. That is, the laminated body 10B has the columnar body 4 and the cavity 5 only in the same layer as that of the positive electrode 1. In the laminated body 10B, the areas where the columnar body 6 and the cavity 7 of the laminated body 10 were present are filled with the same solid electrolyte as the solid electrolyte layer 3. The columnar body 4 can consist of a single layer, as in the first modified example.

[0073] Fig.Figure 7 is a cross-sectional view of a laminated body 10C of a solid-state accumulator according to a third modification example. The laminated body 10C differs from the laminated body 10 in that the columnar body 4 and the cavity 5 are not present. That is, the laminated body 10C has the columnar body 6 and the cavity 7 only in the same layer as that of the negative electrode 2. In this case, the columnar body 6 is an example of the first columnar body. In the laminated body 10C, the areas where the columnar body 4 and the cavity 5 of the laminated body 10 were present are filled with the same solid electrolyte as the solid electrolyte layer 3. The columnar body 6 can consist of a single layer, as in the first modified example.

[0074] As shown in the second and third modification examples, the same effect as with the laminated body 10 is achieved in a case where the columnar body and the cavity are only present in one of the layers of the positive electrode 1 and the negative electrode 2.

[0075] Fig.Figure 8 is a cross-sectional view of a laminated body 10D of a solid-state accumulator according to a fourth modification example. The laminated body 10D differs from the laminated body 10 in that it contains a region 31 containing a solid electrolyte forming the solid electrolyte layer 3, located between the positive electrode 1 and the columnar body 4 in the same layer as that of the positive electrode 1, and a region 32 containing a solid electrolyte forming the solid electrolyte layer 3, located between the negative electrode 2 and the columnar body 6 in the same layer as that of the negative electrode 2. Region 31 is a section in which part of the solid electrolyte layer 3 projects into cavity 5. Region 32 is a section in which part of the solid electrolyte layer 3 projects into cavity 7.Since part of the solid electrolyte layer 3 extends into the cavity 5 and the cavity 7, stresses occurring within the solid electrolyte layer 3 can be reduced.

[0076] In the laminated body 10D, not both regions 31 and 32 need to be present; only one of them may be present. In the laminated body 10D, the columnar body 4 and the columnar body 6 can form a single layer. Furthermore, the laminated body 10D, similar to the second and third modification examples, may contain neither the columnar body 4 nor the columnar body 6.

[0077] Furthermore, Fig.Figure 9 shows a cross-sectional view of a laminated body 10E of a solid-state accumulator according to a fifth modification example. The laminated body 10E differs from the laminated body 10 in that it further includes a columnar body 8 between the positive electrode 1 and the columnar body 4 in the same layer as the positive electrode 1, and further includes a columnar body 9 between the negative electrode 2 and the columnar body 6 in the same layer as the negative electrode 2. The columnar body 8 and the columnar body 9 are examples of third columnar bodies.

[0078] The laminated body 10E has a variety of columnar bodies in the same layer as that of the positive electrode 1 or the negative electrode 2. Although Fig.As shown in Figure 9, where two columnar bodies are located in the same layer, the number of columnar bodies can be three or more. With a large number of columnar bodies in the layer, the force exerted on each columnar body is distributed. As a result, deformations are less likely to occur inside the laminated body.

[0079] The cavity 5 between the positive electrode 1 and the column-shaped body 4 is subdivided by the column-shaped body 8 into cavities 51 and 52. The cavity 7 between the negative electrode 2 and the column-shaped body 6 is subdivided by the column-shaped body 9 into cavities 71 and 72. The column-shaped body 8 can be a single layer or a laminated body with multiple layers. For example, the column-shaped body 8 has the same configuration as the column-shaped body 4. The column-shaped body 9 can be a single layer or a laminated body with multiple layers. For example, the column-shaped body 9 has the same configuration as the column-shaped body 6.

[0080] The laminated body 10E does not necessarily have to contain both columnar bodies 8 and 9; it is also possible to contain only one of them. The laminated body 10E can contain a layer with multiple columnar bodies and a layer with only one columnar body. Furthermore, similar to the second and third modification examples, the laminated body 10E can have no columnar body in the same layer as either the positive electrode 1 or the negative electrode 2.

[0081] Additionally, for example Fig. 10 a cross-sectional view obtained by cutting a solid-state accumulator according to a sixth modification example along the positive electrode 1. Fig.Figure 11 is a cross-sectional view obtained by cutting a solid-state accumulator according to a sixth modification example along the negative electrode 2. Fig. Figure 12 is a cross-sectional view obtained by cutting a laminated body 10F along the xz-plane according to a sixth modification example. Fig. Figure 13 is a cross-sectional view obtained by cutting a laminated body 10F according to a sixth modification example along the yz plane.

[0082] The column-shaped body 4 has a first section 45, a second section 46, and a third section 47. The first section 45 is located in the x-direction of the positive electrode 1, with the cavity 5 enclosed between the first section 45 and the positive electrode 1. The second section 46 is located in the y-direction of the positive electrode 1, with the cavity 55 enclosed between the second section 46 and the positive electrode 1. The third section 47 is located in the y-direction of the positive electrode 1, with the cavity 56 enclosed between the third section 47 and the positive electrode 1. The second section 46 and the third section 47 enclose the positive electrode 1 in the y-direction. A portion of the column-shaped body 4 is located in the y-direction of the positive electrode 1.An example is shown here in which the columnar body 4 is formed by joining the first section 45, the second section 46, and the third section 47; however, the first section 45 and the second section 46, as well as the first section 45 and the third section 47, can also be separate. In the case where they are separate, the second section 46 and the third section 47 are each examples of the fourth columnar body. Regarding the layer configuration, each of the first section 45, the second section 46, and the third section 47 can be a single layer or a section in which a plurality of layers are laminated.

[0083] The column-shaped body 6 has a first section 65, a second section 66, and a third section 67. The first section 65 is located in the y-direction of the negative electrode 2, with the cavity 7 enclosed between the first section 65 and the negative electrode 2. The second section 66 is located in the y-direction of the negative electrode 2, with the cavity 75 enclosed between the second section 66 and the negative electrode 2. The third section 67 is located in the y-direction of the negative electrode 2, with the cavity 76 enclosed between the third section 67 and the negative electrode 2. The second section 66 and the third section 67 enclose the negative electrode 2 in the y-direction. A portion of the column-shaped body 6 is located in the y-direction of the negative electrode 2.An example is shown here in which the columnar body 6 is formed by joining the first section 65, the second section 66, and the third section 67; however, the first section 65 and the second section 66, as well as the first section 65 and the third section 67, can also be separate. In the case where they are separate, the second section 66 and the third section 67 are examples of the fourth columnar body. Regarding the layer configuration, each of the first section 65, the second section 66, and the third section 67 can be a single layer or a section in which a plurality of layers are laminated.

[0084] A width of the first section 65 of the columnar body 6 in the x-direction is designated W1, a width of the cavity 7 in the x-direction as W2, a width of a section in the x-direction in which the positive electrode 1 and the negative electrode 2 overlap when viewed in the z-direction as W3, a width of the cavity 5 in the x-direction as W4, and a width of the first section 45 of the columnar body 4 in the x-direction as W5. In this case, W2 / W1 preferably satisfies 0.07 ≤ W2 / W1 ≤ 15.0, and more preferably 0.14 ≤ W2 / W1 ≤ 7.0. Furthermore, W4 / W5 preferably satisfies 0.07 ≤ W4 / W5 ≤ 15.0, and even more preferably 0.14 ≤ W4 / W5 ≤ 70. If the width of the cavity in the x-direction is large compared to the width of the columnar body in the x-direction, the stresses associated with volume changes during loading and unloading cannot be sufficiently relieved, increasing the risk of cracking.If the width of the cavity in the x-direction is small compared to the width of the columnar body in the x-direction, the risk of a short circuit through the columnar body increases.

[0085] A width of the second section 46 of the columnar body 4 in the y-direction is designated W6, a width of each of the cavities 55 and 75 in the y-direction is designated W7, a width of a section in the y-direction in which the positive electrode 1 and the negative electrode 2 overlap when viewed from the z-direction is designated W8, a width of each of the cavities 56 and 76 in the y-direction is designated W9, and a width of the third section 47 of the columnar body 4 in the y-direction is designated W10. In this case, W7 / W6 preferably satisfies 0.07 ≤ W7 / W6 ≤ 15.0, and more preferably 0.14 ≤ W7 / W6 ≤ 7.0. Furthermore, W9 / W10 preferably satisfies 0.07 ≤ W9 / W10 ≤ 15.0, and even more preferably 0.14 ≤ W9 / W10 ≤ 70.If the width of the cavity in the y-direction is large compared to the width of the columnar body in the y-direction, the stress associated with volume changes during loading and unloading cannot be sufficiently relieved, increasing the risk of cracking. If the width of the cavity in the y-direction is small compared to the width of the columnar body in the y-direction, the risk of a short circuit through the columnar body increases.

[0086] If a portion of the columnar bodies 4 and 6 is present in the y-direction of the positive electrode 1 and the negative electrode 2, the solid electrolyte layer 3 can be supported three-dimensionally, and the concentration of stresses in the solid electrolyte layer 3 can be further suppressed during pressurization and sintering during manufacturing. Furthermore, a cavity in the y-direction of the positive electrode 1 and the negative electrode 2 contained within the solid-state accumulator can further mitigate the stress acting on the interior of the solid-state accumulator.

[0087] Although several modification examples have been described in detail above, the characteristic configurations of the respective modification examples can be combined. In other words, the characteristic configurations of the respective modification examples can be combined to create another modification example. Examples “Example 1” (Production of a paste for the positive electrode)

[0088] The paste for the positive electrode current collector layer was prepared from a powder obtained by mixing Ag, Pd, and LiCoO2 in a mass ratio of 64:16:20. Ethylcellulose and dihydroterpineol were added to this powder and mixed. Ethylcellulose is a binder, and dihydroterpineol is a solvent.

[0089] The paste for the positive electrode active material layer was produced by adding ethylcellulose and dihydroterpineol to LiCoO2 and then mixing. (Production of a paste for the solid electrolyte layer)

[0090] The starting materials Li₂CO₃, SiO₂, and Li₃PO₄ were mixed in a molar ratio of 2:1:1. The mixture was wet-mixed in a ball mill with water as the dispersion medium for 16 hours. The mixture was pre-baked at 950°C for 2 hours to remove Li 3,5 Si 0,5 P 0,5 To produce O4, 100 parts by mass of this pre-baked powder, 100 parts by mass of ethanol, and 200 parts by mass of toluene were placed in a ball mill and wet-mixed. Then, 16 parts by mass of a polyvinyl butyral-based binder and 4.8 parts by mass of benzyl butyl phthalate were added and mixed to produce a paste for the solid electrolyte layer. (Preparation of a paste for the negative electrode)

[0091] The paste for the negative electrode was made from a powder produced by mixing Ag, Pd and Li 3,5 Si 0,5 P 0,5O4 was obtained in a mass ratio of 40:10:50. Ethylcellulose and dihydroterpineol were added to this powder and mixed. (Manufacturing a solid-state accumulator)

[0092] Subsequently, a positive electrode assembly and a negative electrode assembly were fabricated according to the following procedure. First, the paste of the positive electrode active material layer was screen-printed onto the solid electrolyte layer described above. The printed paste of the positive electrode active material layer was then dried at 80°C for 5 minutes. Next, the paste of the positive electrode current collector layer was screen-printed onto the dried paste of the positive electrode active material layer. The printed paste of the positive electrode current collector layer was then dried at 80°C for 5 minutes. Finally, the paste of the positive electrode active material layer was screen-printed again onto the dried paste of the positive electrode current collector layer, and then the drying process was carried out.

[0093] Then, in the same layer as the paste of the positive electrode current collector layer and the paste of the positive electrode active material layer, and at a point spaced x-directed from the paste of the positive electrode current collector layer and the paste of the positive electrode active material layer, a solid electrolyte layer paste, intended to serve as a columnar body, was printed and subsequently dried. Afterward, the PET film was removed. In this way, a positive electrode unit was obtained in which the lamination in the sequence positive electrode active material layer / positive electrode current collector layer / positive electrode active material layer was carried out on the main surface of the solid electrolyte layer, and which had a columnar body formed from the same material as the solid electrolyte layer material.

[0094] Furthermore, a negative electrode assembly, in which a negative electrode was laminated onto the main surface of the solid electrolyte layer, was fabricated using the same method. The negative electrode assembly has a column-shaped body formed from the same material as the solid electrolyte layer, located at a position x-spaced from the negative electrode. This column-shaped body can be produced by printing a paste of the solid electrolyte layer, intended to serve as the column-shaped body, at a position x-spaced from the negative electrode paste in the same layer as the negative electrode paste, and then drying it.In the negative electrode of Example 1, the negative electrode current collector layer and the negative electrode current active material layer are not separated, and AgPd acts as both a negative electrode active material and a negative electrode current collector.

[0095] The solid electrolyte layer paste was then printed and dried several times in a split manner to produce a solid electrolyte unit.

[0096] Subsequently, ten electrode units (five positive and five negative) were stacked alternately to enclose the solid electrolyte unit. In this case, the individual units were shifted and then stacked so that the odd-numbered electrode units (positive electrode units) were exposed on the first surface S1 and the even-numbered electrode units (negative electrode units) were exposed on the second surface S2. Six solid electrolyte films were then layered over the stacked units. The resulting structure was then layered with SUS plates, and the individual units were bonded together using thermocompression bonding and then sliced ​​to create a laminated chip. Finally, the laminated chip underwent simultaneous sintering to produce a laminated body.Simultaneous sintering was carried out by increasing the temperature to a sintering temperature of 800°C with a temperature increase rate of 200°C / hour in an air atmosphere, holding the temperature for 2 hours, and then allowing natural cooling after sintering.

[0097] In the manufactured laminated body, the positive electrode had a thickness of 35 µm, the negative electrode had a thickness of 35 µm, and the solid electrolyte layer had a thickness of 14 µm. Furthermore, the thickness of the columnar body located in the same layer as the positive electrode was 35 µm, and the thickness of the columnar body located in the same layer as the negative electrode was also 35 µm.

[0098] A positive and a negative electrode terminal were then formed on the fabricated laminated body (the battery core). One hundred samples were produced under identical conditions. The cycle characteristics of each sample were then measured. A charge and discharge cycle of the solid-state battery was defined as constant-current charging (CC charging) at a constant current rate of 0.2 C until a battery voltage of 4.0 V was reached, followed by constant-current discharging (CC discharging) at a constant current rate of 0.2 C until a battery voltage of 0 V was reached at an ambient temperature of 25 °C. One hundred cycles of this process were repeated, and the yield of samples with a capacity retention rate of 90% or higher was determined. The capacity conservation rate is determined by "capacity of the solid-state battery at the 1st cycle" / "capacity of the solid-state battery at the 100th cycle" × 100. “Examples 2 to 4”

[0099] Examples 2 to 4 differ from Example 1 in that at least one of the layer configurations of the columnar body located in the same layer as the positive electrode and the columnar body located in the same layer as the negative electrode is different.

[0100] Example 2 differs from Example 1 in that the column-shaped body, which is located in the same layer as the positive electrode, has the same layer configuration as the positive electrode.

[0101] Example 3 differs from Example 1 in that the column-shaped body, which is located in the same layer as the negative electrode, has the same layer configuration as the negative electrode.

[0102] Example 4 differs from Example 1 in that the columnar body located in the same layer as the positive electrode has the same layer configuration as the positive electrode, and the columnar body located in the same layer as the negative electrode has the same layer configuration as the negative electrode. The other configurations were adjusted to be the same as in Example 1, and then the sample yield was determined.

[0103] A columnar body with the same layer configuration as the positive electrode can be produced by simultaneously screen-printing the paste for the positive electrode current collector layer and the paste for the positive electrode active material layer at a location that serves as the columnar part. A columnar body with the same layer configuration as the negative electrode can be produced by simultaneously screen-printing the negative electrode paste at a location that serves as the columnar part. “Examples 5 to 10”

[0104] Examples 5 to 10 differ from Example 4 in that the thickness of the solid electrolyte layer was changed. The other configurations were set as in Example 4, and then the sample yield was determined. The thickness of the solid electrolyte layer was set as follows in each example. Example 5: 4 µm Example 6: 6 µm Example 7: 8 µm Example 8: 10 µm Example 9: 18 µm Example 10: 22 µm “Examples 11 to 15”

[0105] Examples 11 to 15 differ from Example 4 in that the number of electrode units used to fabricate the solid-state accumulator was changed. The other configurations were set as in Example 4, and then the sample yield was determined. The total number of electrodes in the laminated body was set as follows in each example. Example 11: 6 layers Example 12: 20 layers Example 13: 40 layers Example 14: 80 layers Example 15: 120 layers “Examples 16 to 19”

[0106] Examples 16 to 19 differ from Example 4 in that the thickness of the positive electrode was changed. The other configurations were set as in Example 4, and then the sample yield was determined. The thickness of the positive electrode was set as follows in each example. Example 16: 2 µm Example 17: 5 µm Example 18: 10 µm Example 19: 20 µm Example 20: 50 µm “Examples 20 to 25”

[0107] Examples 20 to 25 differ from Example 4 in that the thickness of the negative electrode was changed. The other configurations were set as in Example 4, and then the sample yield was determined. The thickness of the negative electrode was set as follows in each example. Example 20: 2 µm Example 21: 5 µm Example 22: 10 µm Example 23: 20 µm Example 24: 50 µm “Comparison example 1”

[0108] Example 1 differs from Example 11 in that the columnar body was not produced. The other configurations were set as in Example 11, and then the sample yield was determined. “Comparative examples 2 to 7”

[0109] Comparison examples 2 to 7 differ from comparison example 1 in that the thickness of the solid electrolyte layer was changed. The other configurations were set as in comparison example 1, and then the sample yield was determined. The thickness of the solid electrolyte layer was set as follows in each comparison example. Comparison example 2: 18 µm Comparative example 3: 14 µm Comparative example 4: 10 µm Comparative example 5: 8 µm Comparative example 6: 6 µm Comparative example 7: 4 µm “Comparative examples 8 to 10”

[0110] Comparison examples 8 to 10 differ from comparison example 3 in that the number of electrode units used for fabricating the solid-state accumulator was changed. The other configurations were set as in comparison example 3, and then the sample yield was determined. The total number of electrodes in the laminated body was set as follows in each comparison example. Comparison example 8: 6 layers Comparison example 9: 3 layers Comparison example 10: 2 layers “Comparative examples 11 to 15”

[0111] Comparison examples 11 to 15 differ from comparison example 3 in that the thickness of the positive electrode was changed. The other configurations were set as in comparison example 3, and then the sample yield was determined. The thickness of the positive electrode was set as follows in each comparison example. Comparative example 11: 2 µm Comparative example 12: 5 µm Comparative example 13: 10 µm Comparative example 14: 20 µm Comparative example 15: 50 µm “Comparative examples 16 to 20”

[0112] Comparison examples 16 to 20 differ from comparison example 3 in that the thickness of the negative electrode was changed. The other configurations were set as in comparison example 3, and then the sample yield was determined. The thickness of the negative electrode was set as follows in each example. Comparative example 16: 2 µm Comparative example 17: 5 µm Comparative example 18: 10 µm Comparative example 19: 20 µm Comparative example 20: 50 µm

[0113] The results of Examples 1 to 24 and Comparative Examples 1 to 20 are summarized in Tables 1 to 4 below. In Tables 1 to 4, L1 represents the thickness of the positive electrode, L2 the thickness of the negative electrode, and L3 the thickness of the solid electrolyte layer. [Table 1] Column-shaped body in the same layer as the layer of the positive electrode Column-shaped body in the same layer as the layer of the negative electrode Positive electrode solid electrolyte layer Negative electrode L1 / L3 L2 / L3 Number of laminations of the laminated body Yield (%) Number of layers Material of the columnar body Number of layers Material of the column-shaped body (µm) (µm) (µm) Example 1 Single layer Same as the material of the solid electrolyte layer Single layer Same as the material of the solid electrolyte layer 35 14 35 2.5 2.5 10 98 Example 2 Three layers Same as the material of the three layers of the positive electrode Single layer Same as the material of the solid electrolyte layer 35 14 35 2.5 2.5 10 98 Example 3 Single layer Same as the material of the solid electrolyte layer Single layer Just like with a dernepative electrode 35 14 35 2.5 2.5 10 98 Example 4 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 10 99 Example 5 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 4 35 8.8 8.8 10 92 Example 6 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 6 35 5.8 5.8 10 94 Example 7 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 8 35 4.4 4.4 10 95 Example 8 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 10 35 3.5 3.5 10 97 Example 9 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 18 35 1.9 1.9 10 99 Example 10 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 22 35 1.6 1.6 10 99 Example 11 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 6 99 Example 12 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 20 99 Example 13 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 40 99 Example 14 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 80 99 Example 15 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 35 2.5 2.5 120 99 [Table 2] Column-shaped body in the same layer as the layer of the positive electrode Column-shaped body in the same layer as the layer of the negative electrode Positive electrode solid electrolyte layer Negative electrode L1 / L3 L2 / L3 Number of laminations of the laminated body Exploitation (%) Number of layers Material of the columnar body Number of layers Material of the column-shaped body (µm) (µm) (µm) Example 16 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 2 14 35 0.1 2.5 10 99 Example 17 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 5 14 35 0.4 2.5 10 99 Example 18 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 10 14 35 0.7 2.5 10 99 Example 19 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 20 14 35 1.4 2.5 10 99 Example 20 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 50 14 35 3.6 2.5 10 99 Example 21 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 2 2.5 0.1 10 99 Example 22 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 5 2.5 0.4 10 99 Example 23 Three layers Same as the material of the three layers of the positive electrode Single layer Just like with the negative electrode 35 14 10 2.5 0.7 10 99 Example 24 Three layers Same material as both three layers of the positive electrode Single layer Just like with the negative electrode 35 14 20 2.5 1.4 10 99 Example 25 Three layers Same material as both three layers of the positive electrode Single layer Just like with the negative electrode 35 14 50 2.5 3.6 10 99 [Table 3] Columnar body in the same layer as the layer of the positive electrode Columnar body in the same layer as the layer of the negative electrode Positive electrode solid electrolyte layer Negative electrode L1 / L3 L2 / L3 Number of laminations of the laminated body Yield(%) Number of layers Material of the column-shaped body Number of layers Material of the column-shaped body (µm) (µm) (µm) Comparative example 1 No No 35 22 35 1.6 1.6 10 88 Comparative example 2 No No 35 18 35 1.9 1.9 10 83 Comparative example 3 No No 35 14 35 2.5 2.5 10 43 Comparative example 4 No No 35 10 35 3.5 3.5 10 33 Comparative example 5 No No 35 8 35 4.4 4.4 10 31 Comparative example 6 No No 35 6 35 5.8 5.8 10 25 Comparative example 7 No No 35 4 35 8.8 8.8 10 20 Comparative example 8 No No 35 14 35 2.5 2.5 6 55 Comparative example 9 No No 35 14 35 2.5 2.5 3 63 Comparative example 10 No No 35 14 35 2.5 2.5 2 81 [Table 4] Columnar body in the same layer as the layer of the positive electrode Columnar body in the same layer as the layer of the negative electrode Positive electrode solid electrolyte layer Negative electrode L1 / L3 L2 / L3 Number of laminations of the laminated body Yield(%) Number of layers Material of the column-shaped body Number of layers Material of the column-shaped body (µm) (µm) (µm) Comparative example 11 No No 2 14 35 0.1 2.5 10 79 Comparative example 12 No No 5 14 35 0.4 2.5 10 77 Comparative example 13 No No 10 14 35 0.7 2.5 10 45 Comparative example 14 No No 20 14 35 1.4 2.5 10 45 Comparative example 15 No No 50 14 35 3.6 2.5 10 23 Comparative example 16 No No 35 14 2 2.5 0.1 10 82 Comparative example 17 No No 35 14 5 2.5 0.4 10 80 Comparative example 18 No No 35 14 10 2.5 0.7 10 47 Comparative example 19 No No 35 14 20 2.5 1.4 10 45 Comparative example 20 No No 35 14 50 2.5 3.6 10 26

[0114] As can be seen from Tables 1 to 4, examples 1 to 24 all had a higher yield than the comparison examples 1 to 20. That is, by providing the column-shaped body in the same layer as that of the positive or negative electrode, it was less likely that cracks would occur inside the solid-state accumulator.

[0115] As shown in comparative examples 1 to 7 and 11 to 20, the yield tends to decrease with increasing thickness of the positive or negative electrode relative to the thickness of the solid electrolyte layer when the column-shaped body is absent. This is presumed to be due to the fact that the gap between the solid electrolyte layers increases with the thickness of the positive or negative electrode. Without the column-shaped body, it is assumed that the solid electrolyte layer deforms in the direction of the gap between the solid electrolyte layers, likely resulting in cracks in the solid-state accumulator.

[0116] On the other hand, Examples 5 to 10 and 16 to 25 showed that the presence of the column-shaped body does not result in a significant difference in yield, even when the thickness of the positive or negative electrode is greater than the thickness of the solid electrolyte layer. This is likely because the column-shaped body supports a gap between adjacent solid electrolyte layers, thus reducing the likelihood of deformation. In other words, the thicker the positive or negative electrode, the more effectively the column-shaped body functions, thereby preventing cracks in the solid-state accumulator.

[0117] As shown in comparative examples 8 to 10, in a case where the column-shaped body was not present, the yield tended to decrease as the total number of positive and negative electrodes increased. This is thought to be because, with an increasing total number of positive and negative electrodes, deformation is more likely to occur at the end portion of the laminated body. On the other hand, as shown in examples 11 to 15, providing a column-shaped body can ensure a sufficient yield even when the total number of laminated bodies increases. (Examples 26 to 58)

[0118] In examples 26 to 58, a solid-state accumulator of the type in Fig. 10 to Fig.The sixth modification example shown in Figure 13 is produced. Examples 26 to 58 differ from Example 2 in that the paste, which would serve as a columnar body, was also formed in the sections that would serve as the second sections 46 and 66 and the third sections 47 and 67, which are shown in Fig. 10 and Fig. 11 are shown. The other conditions were the same as in Example 2.

[0119] In Examples 26 to 58, the columnar body located in the same layer as the positive electrode has the same layer configuration as the positive electrode. In Examples 26 to 57, the columnar body located in the same layer as the negative electrode was fabricated using a solid electrolyte paste. The thickness of the positive electrode was set to 35 µm, the thickness of the negative electrode to 35 µm, and the thickness of the solid electrolyte layer to 14 µm. Furthermore, the thickness of the columnar body located in the same layer as the positive electrode was set to 35 µm, as was the thickness of the columnar body located in the same layer as the negative electrode. Additionally, the total number of electrodes in the laminated body was set to 10 layers.

[0120] In Examples 26 to 58, the width W1 of the first section 65 of the columnar body 6 in the x-direction, the width W2 of the cavity 7 in the x-direction, the width W3 of the section in the x-direction where the positive electrode 1 and the negative electrode 2 overlap when viewed from the z-direction, the width W4 of the cavity 5 in the x-direction, the width W5 of the first section 45 of the columnar body 4 in the x-direction, the width W6 of the second section 46 of the columnar body 4 in the y-direction, the width W7 of each of the cavities 55 and 75 in the y-direction, the width W8 of the section in the y-direction where the positive electrode 1 and the negative electrode 2 overlap when viewed in the z-direction, and the width W9 of each of the cavities 56 and 76 in the y-direction were measured. y-direction, and the width W10 of the third section 47 of the columnar body 4 in the y-direction was changed.

[0121] The results for examples 26 to 58 are summarized in Table 5 and Table 6. [Table 5] [Table 6] REFERENCE MARK LIST 1 Positive electrode 11 Positive electrode current collector layer 12 Positive electrode active material layer 1A First positive electrode 1B Second positive electrode 2 Negative electrode 21 Negative electrode current collector layer 22 Negative electrode active material layer 2A First negative electrode 2B Second negative electrode 3 Solid electrolyte layer 4, 6 Columnar body 5, 7 cavity 5A First cavity 5B Second cavity 41, 61 First shift 42, 62 Second shift 10, 10A, 10B, 10C Laminated body 80 Positive electrode connection 90 Negative electrode connection 100 solid-state accumulator S1 First surface S2 Second Surface S3 Third Surface S4 Fourth Surface QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2022-203082

[0001] WO 2008 / 099508

[0004]

Claims

[1] A solid-state accumulator comprising: a positive electrode; a negative electrode; a solid electrolyte layer between the positive electrode and the negative electrode; and a first column-shaped body located in the same layer as the positive electrode or the negative electrode and spaced apart from the positive electrode or the negative electrode, with a cavity enclosed between the first column-shaped body and the positive electrode or the negative electrode. [2] The solid-state accumulator according to claim 1, wherein the first column-shaped body is spaced apart from the positive electrode in the same layer as the positive electrode, the cavity between the first column-shaped body and the positive electrode being enclosed. [3] The solid-state accumulator according to claim 2, further comprising: a second column-shaped body, wherein the second column-shaped body is spaced apart from the negative electrode in the same layer as the negative electrode, with a cavity enclosed between the second column-shaped body and the negative electrode. [4] The solid-state accumulator according to claim 1, further comprising: a positive electrode connection and a negative electrode connection, wherein the positive electrode terminal is connected to the positive electrode on a first surface of a laminated body comprising the positive electrode, the negative electrode and the solid electrolyte layer, the negative electrode terminal is connected to the negative electrode on a second surface of the laminated body, which differs from the first surface, and the first column-shaped body is present between the positive electrode terminal and the negative electrode or between the negative electrode terminal and the positive electrode. [5] The solid-state accumulator according to claim 4, wherein the positive electrode terminal is in contact with the first surface and a surface adjacent to the first surface, and the positive electrode terminal is not in contact with the negative electrode. [6] The solid-state accumulator according to claim 4, wherein the negative electrode terminal is in contact with the second surface and a surface adjacent to the second surface, and the negative electrode terminal is not in contact with the positive electrode. [7] The solid-state accumulator according to claim 1, wherein the first column-shaped body has the same layer configuration as the positive electrode or the negative electrode. [8] The solid-state accumulator according to claim 1, wherein the thickness of the positive electrode is 2.5 times or more in relation to the thickness of the solid electrolyte layer. [9] The solid-state accumulator according to claim 1, wherein the thickness of the negative electrode is 2.5 times or more in relation to the thickness of the solid electrolyte layer. [10] The solid-state accumulator according to claim 1, wherein the positive electrode has a thickness of 10 µm or more. [11] The solid-state accumulator according to claim 1, wherein the negative electrode has a thickness of 10 µm or more. [12] The solid-state accumulator according to claim 1, wherein the positive electrode is at least one layer, the negative electrode is at least one layer, and a total number of positive electrodes and negative electrodes is 3 or more. [13] The solid-state accumulator according to claim 1, wherein a laminated body comprising the positive electrode, the negative electrode and the solid electrolyte layer has a first positive electrode and a second positive electrode adjacent to each other in a lamination direction, and a first cavity located between the first positive electrode and the column-shaped body in the same layer as the first positive electrode, and a second cavity located between the second positive electrode and the column-shaped body in the same layer as the second positive electrode, overlap at least partially when viewed from the lamination direction of the laminated body. [14] The solid-state accumulator according to claim 13, wherein 80% or more of the first cavity overlaps with the second cavity when viewed from the lamination direction of the laminated body. [15] The solid-state accumulator according to claim 1, wherein a laminated body comprising the positive electrode, the negative electrode and the solid electrolyte layer has a first negative electrode and a second negative electrode adjacent to each other in a lamination direction, and a third cavity located between the first negative electrode and the column-shaped body in the same layer as the first negative electrode, and a fourth cavity located between the second negative electrode and the column-shaped body in the same layer as the second negative electrode, overlap at least partially when viewed from the lamination direction of the laminated body. [16] The solid-state accumulator according to claim 15, wherein 80% or more of the third cavity overlaps with the fourth cavity when viewed from the lamination direction of the laminated body. [17] The solid-state accumulator according to claim 1, further comprising: a first area containing a solid electrolyte, forming the solid electrolyte layer between the positive electrode or the negative electrode and the first column-shaped body, in the same layer as that of the positive electrode or the negative electrode. [18] The solid-state accumulator according to claim 1, further comprising: a third column-shaped body between the positive electrode or the negative electrode and the first column-shaped body in the same layer as that of the positive electrode or the negative electrode. [19] The solid-state accumulator according to claim 1, wherein in a case where a direction from the first column-shaped body to the positive electrode or the negative electrode in the same layer as that of the positive electrode or the negative electrode is defined as a first direction, including the cavity between the first column-shaped body and the positive electrode or the negative electrode, and a direction intersecting the first direction is defined as a second direction, a part of the first column-shaped body or a fourth column-shaped body is present at a position in the second direction of the positive electrode or the negative electrode. [20] The solid-state accumulator according to claim 1, wherein in a case where a direction from the first column-shaped body to the positive electrode or the negative electrode in the same layer as that of the positive electrode or the negative electrode is defined as a first direction, wherein the cavity between the first column-shaped body and the positive electrode or the negative electrode is included, a width of the cavity in the first direction is 0.07 times or more or 15.0 times or less with respect to a width of the first column-shaped body in the first direction.

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