All-solid-state battery and method for manufacturing all-solid-state battery

Abstract

To provide a full-solid-state battery capable of improving battery characteristics and a manufacturing method of the full-solid-state battery. A full-solid-state battery (1) is a full-solid-state battery in which a negative electrode layer (10) and a positive electrode layer (20) having a positive electrode active material layer (25) are stacked with a solid electrolyte layer (30) interposed therebetween. An insulating layer (26) is provided at an outer peripheral portion of the positive electrode active material layer (25). The full-solid-state battery (1) is provided with a bonding layer (50) provided between the insulating layer (26) and the solid electrolyte layer (30) adjacent to the insulating layer (26).

Description

Technical Field

[0001] This invention relates to an all-solid-state battery and a method for manufacturing an all-solid-state battery. Background Technology

[0002] In recent years, research and development on rechargeable batteries has been underway to help improve energy efficiency, in order to ensure that more people have access to affordable, reliable, sustainable and advanced energy.

[0003] In secondary batteries, all-solid-state batteries using solid electrolytes are attracting attention due to their superior safety profile caused by the non-flammability of solid electrolytes and their higher energy density. As an all-solid-state battery, all-solid-state batteries with a stacked structure are being researched, wherein multiple positive electrode layers and negative electrode layers are alternately stacked with a solid electrolyte layer in between (e.g., Patent Document 1).

[0004] In Patent Document 1, the positive electrode layer is formed by stacking a positive electrode current collector layer and a positive electrode active material layer. An insulating frame is provided on the outer periphery of the positive electrode active material layer to suppress the generation of short circuits. The insulating frame is disposed opposite to the solid electrolyte layer.

[0005] [Existing Technical Documents]

[0006] [Patent Literature]

[0007] Patent Document 1: Japanese Patent Application Publication No. 2023-47083 Summary of the Invention

[0008] [The problem the invention aims to solve]

[0009] The insulating frame and the solid electrolyte layer are both formed of relatively rigid materials. The solid electrolyte layer is prone to sliding relative to the insulating frame. When the solid electrolyte layer is stacked with the positive electrode layer, the solid electrolyte layer may slide relative to the insulating frame, causing the positional relationship between the solid electrolyte layer and the positive electrode layer to deviate from the ideal relationship. In this case, the resistance between the positive electrode layer and the solid electrolyte layer will increase, which may impair the battery characteristics of the all-solid-state battery.

[0010] The objective of this invention is to provide an all-solid-state battery capable of improving battery characteristics and a method for manufacturing the all-solid-state battery.

[0011] [Technical means to solve the problem]

[0012] (1) The present invention is an all-solid-state battery, which is formed by stacking a negative electrode layer and a positive electrode layer having a positive electrode active material layer in between a solid electrolyte layer. An insulating layer is provided on the outer periphery of the aforementioned positive electrode active material layer, and an adhesive layer is provided. The adhesive layer is disposed between the aforementioned insulating layer and the aforementioned solid electrolyte layer adjacent to the insulating layer.

[0013] According to the all-solid-state battery described in (1), since the adhesive layer is disposed between the insulating layer and the solid electrolyte layer, the sliding of the insulating layer relative to the solid electrolyte layer can be suppressed. Therefore, the deviation of the positional relationship between the solid electrolyte layer and the positive electrode active material layer from the ideal positional relationship can be suppressed, thereby suppressing the increase in resistance between the solid electrolyte layer and the positive electrode active material layer. Therefore, an all-solid-state battery 1 with improved battery characteristics can be provided.

[0014] (2) The all-solid-state battery according to (1) above, wherein the aforementioned insulating layer may also be formed of aluminum oxide.

[0015] According to the all-solid-state battery described in (2), since alumina is a low-conductivity material, the insulation performance of the insulating layer can be improved. Therefore, when the negative electrode layer (negative electrode tab) bends and contacts the insulating layer, short circuits between the negative and positive electrode layers can be effectively suppressed. Furthermore, when the insulating layer is formed of alumina, it becomes harder and may easily slide relative to the solid electrolyte layer. However, thanks to the adhesive layer, sliding of the insulating layer relative to the solid electrolyte layer can be suppressed, making it easier to use alumina as the insulating layer material.

[0016] (3) According to the all-solid-state battery described in (1) or (2) above, wherein the direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked with the aforementioned solid electrolyte layer in between is set as the stacking direction, one of the directions orthogonal to the aforementioned stacking direction is set as the first direction, and the direction orthogonal to the aforementioned stacking direction and the aforementioned first direction is set as the second direction, the aforementioned positive electrode active material layer has the aforementioned first direction as its length direction, the aforementioned insulating layer has a first side extending along the aforementioned second direction, and the aforementioned adhesive layer may also be disposed between the aforementioned first side and the aforementioned solid electrolyte layer.

[0017] According to the all-solid-state battery described in (3), the slippage of the solid electrolyte layer relative to the insulating layer can be effectively suppressed. Therefore, the deviation of the positional relationship between the solid electrolyte layer and the positive electrode layer from the ideal positional relationship can be effectively suppressed.

[0018] (4) In the all-solid-state battery according to (1) or (2) above, the aforementioned adhesive layer may also be disposed only between the aforementioned first side and the aforementioned solid electrolyte layer.

[0019] According to the all-solid-state battery described in (4), the sliding of the solid electrolyte layer relative to the insulating layer can be effectively suppressed, and the amount of adhesive layer used can be suppressed.

[0020] (5) The all-solid-state battery according to (3) above, wherein the aforementioned insulating layer has a second side portion, the second side portion is adjacent to the aforementioned first side portion in the aforementioned first direction and extends along the aforementioned first direction, and the aforementioned adhesive layer may also be disposed between the aforementioned second side portion and the aforementioned solid electrolyte layer.

[0021] According to the all-solid-state battery described in (5), the slippage of the solid electrolyte layer relative to the insulating layer can be more effectively suppressed.

[0022] (6) The all-solid-state battery according to any one of (1) to (5), wherein the aforementioned adhesive layer may also be in the form of dots.

[0023] According to the all-solid-state battery described in (6), the sliding of the solid electrolyte layer relative to the insulating layer can be effectively suppressed, and the amount of adhesive layer used can be suppressed.

[0024] (7) According to the all-solid-state battery described in (1) above, the direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked with respect to the aforementioned solid electrolyte layer is set as the stacking direction, and a recessed portion that is recessed in the aforementioned stacking direction may also be formed in the portion of the aforementioned insulating layer that overlaps with the aforementioned adhesive layer in the aforementioned stacking direction.

[0025] According to the all-solid-state battery described in (7), when the adhesive layer is in contact with the solid electrolyte layer, the positive electrode active material layer can be easily contacted with the solid electrolyte layer, thereby making it easy for electrons to migrate between the positive electrode active material layer and the solid electrolyte layer.

[0026] (8) The all-solid-state battery according to (1) above, wherein the aforementioned stacking direction dimension of the aforementioned recess is more than 65% and less than 100% of the aforementioned stacking direction dimension of the aforementioned insulating layer.

[0027] According to the all-solid-state battery described in (8), if the stacking dimension of the insulating layer becomes smaller, the strength of the insulating layer may decrease. If the stacking dimension of the adhesive layer becomes smaller, the strength of the adhesive layer may decrease. However, by adopting the aforementioned structure, the strength of the insulating layer can be ensured while the strength of the adhesive layer is also ensured.

[0028] (9) The present invention is a method for manufacturing an all-solid-state battery, which is the method for manufacturing an all-solid-state battery described in (1) above, comprising: a preparation step of preparing a positive electrode layer with an insulating layer, the positive electrode layer with an insulating layer having a positive electrode active material layer and an insulating layer disposed on the outer periphery of the positive electrode active material layer; an adhesive layer configuration step of configuring an adhesive layer on the surface of the aforementioned insulating layer; a solid electrolyte layer configuration step of configuring a solid electrolyte layer on the surface of the aforementioned positive electrode layer with an insulating layer; and a negative electrode layer configuration step of stacking a negative electrode layer on the surface of the aforementioned solid electrolyte layer opposite to the side of the aforementioned positive electrode layer.

[0029] According to the manufacturing method of the all-solid-state battery described in (9), by stacking an insulating layer on the surface of the positive electrode layer to form an insulating positive electrode layer, and by placing a solid electrolyte layer on the surface of the insulating positive electrode layer, it is possible to suppress the deviation of the positional relationship between the solid electrolyte layer and the positive electrode active material layer from the ideal positional relationship. This suppresses the increase in resistance between the solid electrolyte layer and the positive electrode active material layer, thus providing a manufacturing method for an all-solid-state battery that improves battery characteristics.

[0030] (10) The manufacturing method of the all-solid-state battery according to (9) above may also be carried out as follows: in the solid electrolyte layer configuration step, the direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked with respect to the aforementioned solid electrolyte layer is set as the stacking direction, one of the directions orthogonal to the aforementioned stacking direction is set as the first direction, and the direction orthogonal to the aforementioned stacking direction and the aforementioned first direction is set as the second direction. In the aforementioned preparation step, the aforementioned positive electrode active material layer with the aforementioned first direction set as the length direction and the aforementioned insulating layer having a first side extending along the aforementioned second direction are prepared. In the aforementioned adhesive layer configuration step, the aforementioned adhesive layer is configured on the aforementioned first side.

[0031] According to the manufacturing method of the all-solid-state battery described in (10), it is possible to manufacture an all-solid-state battery that can sufficiently suppress the slippage of the solid electrolyte layer relative to the insulating layer.

[0032] (11) In the method for manufacturing an all-solid-state battery according to (10) above, the adhesive layer may be disposed only on the first side in the aforementioned adhesive layer configuration step.

[0033] According to the manufacturing method of the all-solid-state battery described in (11), an all-solid-state battery that can sufficiently suppress the slippage of the solid electrolyte layer relative to the insulating layer can be obtained, and the amount of adhesive layer used can be suppressed.

[0034] (12) The manufacturing method of the all-solid-state battery according to (10) above may also be carried out as follows: in the aforementioned preparation step, a positive electrode layer with an insulating layer is prepared, wherein the positive electrode layer with an insulating layer further has a second side adjacent to the aforementioned first side in the aforementioned first direction and extending along the aforementioned first direction, and in the aforementioned adhesive layer configuration step, the aforementioned adhesive layer is configured on the aforementioned second side.

[0035] According to the manufacturing method of the all-solid-state battery described in (12), it is possible to manufacture an all-solid-state battery that more effectively suppresses the slippage of the solid electrolyte layer relative to the insulating layer.

[0036] (13) The manufacturing method of the all-solid-state battery described in (9) to (12) above may also include a positive electrode winding step, wherein the positive electrode winding step winds the laminate into a roll, and the laminate is formed by stacking the aforementioned positive electrode layer and the aforementioned solid electrolyte layer, wherein the aforementioned insulating layer is disposed thereon, by interposing the aforementioned adhesive layer between the aforementioned insulating layer and the aforementioned solid electrolyte layer.

[0037] According to the manufacturing method of the all-solid-state battery described in (13), all-solid-state batteries can be manufactured efficiently. On the other hand, when rolling the stack of solid electrolyte layer and positive electrode layer into a roll in multiple all-solid-state batteries, if the positional relationship between the solid electrolyte layer and the positive electrode layer deviates from the ideal positional relationship, it may be difficult to roll the stack of solid electrolyte layer and positive electrode layer into a roll. However, by intervening an adhesive layer between the insulating layer and the solid electrolyte layer, the deviation of the positional relationship between the solid electrolyte layer and the positive electrode layer can be suppressed by the adhesive layer, thereby making it easier to roll the stack of solid electrolyte layer and positive electrode layer into a roll. As a result, all-solid-state batteries can be manufactured more efficiently.

[0038] [Invention Effects]

[0039] According to the present invention, an all-solid-state battery with improved battery characteristics can be provided.

[0040] According to the present invention, a method for manufacturing an all-solid-state battery that can improve battery characteristics can be provided. Attached Figure Description

[0041] Figure 1 This is a perspective view of the all-solid-state battery according to the implementation method.

[0042] Figure 2 It is along Figure 1 A cross-sectional view of the all-solid-state battery in the II-II line.

[0043] Figure 3 It is along Figure 1 A cross-sectional view of the all-solid-state battery in line III-III.

[0044] Figure 4 This is an exploded 3D view of an all-solid-state battery.

[0045] Figure 5 It is a top view of the cathode layer observed along the stacking direction.

[0046] Figure 6 It is a top view of the positive electrode layer with the adhesive layer stacked along the stacking direction.

[0047] Figure 7 This is a step diagram illustrating the manufacturing method of an all-solid-state battery according to an embodiment.

[0048] Figure 8This is a top view of a modified example of a positive electrode layer with a bonding layer, viewed along the stacking direction.

[0049] Figure 9 This is a top view of a modified example of a positive electrode layer with a bonding layer, viewed along the stacking direction.

[0050] Figure 10 This is a top view of a modified example of a positive electrode layer with a bonding layer, viewed along the stacking direction. Detailed Implementation

[0051] Hereinafter, an all-solid-state battery 1 according to an embodiment of the present invention will be described. There is no particular limitation on the type of all-solid-state battery 1; for example, it may be an all-solid-state lithium battery using lithium ions as the charge transfer medium. Figures 1-4 As shown, the all-solid-state battery 1 has a structure in which a positive electrode layer 20 and a negative electrode layer 10 are stacked in a layer of solid electrolyte layer 30.

[0052] In this specification, the direction in which the positive electrode layer 20 and the negative electrode layer 10 are stacked, separated by the solid electrolyte layer 30, is designated as the "T direction". The T direction is equivalent to the stacking direction. One of the directions orthogonal to the T direction is designated as the "X direction". The X direction is equivalent to the first direction. The direction orthogonal to both the T and X directions is designated as the "Y direction". The Y direction is equivalent to the second direction. One side of the X direction is designated as the "X+ direction", and the opposite side of the X+ direction is designated as the "X- direction".

[0053] (All-solid-state battery)

[0054] The all-solid-state battery 1, for example, comprises multiple negative electrode layers 10, multiple solid electrolyte layers 30, and multiple positive electrode layers 20. The negative electrode layers 10, solid electrolyte layers 30, positive electrode layers 20, and solid electrolyte layers 30 are stacked sequentially. The total number of negative electrode layers 10 and positive electrode layers 20 is not particularly limited, but is preferably 10 or more. Furthermore, in... Figures 2-4 The illustrations near each end of the all-solid-state battery 1 in the T direction are omitted.

[0055] The all-solid-state battery 1 includes an outer casing 5, a negative electrode tab lead 6, and a positive electrode tab lead 7. The outer casing 5 is disposed on the surface of the all-solid-state battery 1. The outer casing 5 covers a laminate of a negative electrode layer 10, a solid electrolyte layer 30, and a positive electrode layer 20. The outer casing 5 is formed, for example, from resin. Figure 1 In the diagram, the outer casing 5 is indicated by a double-dotted line. The negative electrode lead 6 is connected to the bundled negative electrode 14 (described later). The negative electrode lead 6 extends out from the outer casing 5. The positive electrode lead 7 is connected to the bundled positive electrode 24 (described later). The positive electrode lead 7 extends out from the outer casing 5.

[0056] (Negative electrode layer)

[0057] The negative electrode layer 10 has a negative electrode active material layer 15 and a negative electrode current collector layer 11. For example, a negative electrode layer 10 has a negative electrode current collector layer 11 and two negative electrode active material layers 15 disposed in the T direction sandwiching the negative electrode current collector layer 11.

[0058] The negative electrode active material layer 15 contains a negative electrode active material. Examples of negative electrode active materials include lithium metal, lithium alloys, silicon (Si) and silicon alloys, and lithium titanate (Li4Ti5O4). 12 The active material layer 15 is preferably composed of lithium metal, including lithium transition metal oxides such as TiO2, Nb2O3, and WO3, metal sulfides, metal nitrides, carbon materials such as graphite, soft carbon, and hard carbon, and indium. The active material layer 15 may further include a solid electrolyte, conductive additives, and binders.

[0059] The shape of the negative electrode active material layer 15 is, for example, a plate extending along the X and Y directions. The shape of the negative electrode active material layer 15 viewed along the T direction is, for example, a rectangle with its long side extending along the X direction.

[0060] The negative electrode current collector layer 11 is disposed adjacent to the negative electrode active material layer 15. The negative electrode current collector layer 11 is not particularly limited, and may be made of copper for example. The shape of the negative electrode current collector layer 11 may be, for example, foil-shaped. The negative electrode current collector layer 11 has a negative electrode current collector layer body portion 12 and a negative electrode tab 14.

[0061] The negative electrode current collector layer main body 12 is the portion of the negative electrode current collector layer 11 that overlaps with the adjacent negative electrode active material layer 15 in the T direction. The shape of the negative electrode current collector layer main body 12 when viewed along the T direction is, for example, a roughly rectangular shape with its long side extending along the X direction.

[0062] The negative electrode tab 14 is a portion of the negative electrode current collector layer 11 that extends in a specific direction from the main body 12 of the negative electrode current collector layer. The negative electrode tab 14 extends, for example, from the main body 12 of the negative electrode current collector layer in the X direction (specifically, the X-direction). The Y-direction dimension of the negative electrode tab 14 is smaller than the Y-direction dimension of the main body 12 of the negative electrode current collector layer. The shape of the negative electrode tab 14 when viewed along the T direction is, for example, a generally rectangular shape with its long side extending along the X direction. The front ends of a plurality of negative electrode tabs 14 are clustered together.

[0063] (Solid electrolyte layer)

[0064] A solid electrolyte layer 30 is disposed between the negative electrode layer 10 and the positive electrode layer 20. The solid electrolyte layer 30 contains a solid electrolyte material. Examples of solid electrolyte materials include sulfide solid electrolyte materials and oxide solid electrolyte materials.

[0065] (Positive electrode layer)

[0066] The positive electrode layer 20 has a positive electrode active material layer 25 and a positive electrode current collector layer 21. For example, a positive electrode layer 20 has one positive electrode current collector layer 21 and two positive electrode active material layers 25 disposed in the T direction sandwiching the positive electrode current collector layer 21.

[0067] The positive electrode active material layer 25 contains a positive electrode active material. Examples of positive electrode active materials include transition metal chalcogenides such as titanium disulfide, molybdenum disulfide, and niobium selenide, as well as transition metal oxides such as lithium nickel oxide (LiNiO2), lithium manganese oxide (LiMnO2, LiMn2O4), and lithium cobalt oxide (LiCoO2). The positive electrode active material layer 25 may further contain a solid electrolyte, conductive additives, and binders.

[0068] The positive electrode active material layer 25 may have the shape of, for example, a flat plate extending along the X and Y directions. The shape of the positive electrode active material layer 25 viewed along the T direction may have the shape of, for example, a rectangle with its long side extending along the X direction.

[0069] An insulating layer 26 is provided on the outer periphery of the positive electrode active material layer 25.

[0070] The insulating layer 26 comprises a material with electronic insulating properties. Examples of such electronically insulating materials include insulating oxides such as alumina, resins such as polyvinylidene fluoride (PVDF), and rubbers such as styrene-butadiene rubber (SBR). The insulating layer 26 is preferably formed of alumina. Alternatively, the insulating layer 26 may also have ionic conductivity.

[0071] The insulating layer 26 is generally flat, extending along the X and Y directions. The shape of the insulating layer 26 when viewed along the T direction is, for example, a generally rectangular frame with its long side extending along the X direction (see reference). Figure 5 The insulating layer 26 has, for example, a pair of first sides 27 opposite each other in the X direction; and a pair of second sides 28 opposite each other in the Y direction and sandwiched between the first sides 27.

[0072] The shape of each first side 27, when viewed along the T direction, is a strip with the Y direction as its length. The shape of each second side 28, when viewed along the T direction, is a strip with the X direction as its length. The length dimension of the first side 27 is less than the sum of the length dimensions of the short side of the first side 27 and the length dimensions of the second side 28. The length dimension of the first side 27 is, for example, less than the length dimension of the second side 28.

[0073] According to the insulating layer 26, short circuits of the all-solid-state battery 1 can be suppressed, or the strength of the all-solid-state battery 1 can be improved.

[0074] The positive electrode current collector layer 21 is disposed adjacent to the positive electrode active material layer 25. The positive electrode current collector layer 21 is formed of a current collector. Examples of current collectors include aluminum, copper, nickel, vanadium, iron, titanium, stainless steel, gold, platinum, and carbon. For example, the positive electrode current collector layer 21 is formed of aluminum. The shape of the positive electrode current collector layer 21 is, for example, foil-shaped. The positive electrode current collector layer 21 has a positive electrode current collector layer body portion 22 and a positive electrode tab 24.

[0075] The positive current collector layer main body 22 is the portion of the positive current collector layer 21 that overlaps with the positive active material layer 25 adjacent to the positive current collector layer 21 in the T direction. More specifically, it is the portion that overlaps with at least one of the two positive active material layers 25 adjacent to the positive current collector layer 21 in the T direction. The shape of the positive current collector layer main body 22 when viewed along the T direction is, for example, a rectangle with its long side extending along the X direction.

[0076] Furthermore, when an insulating layer 26 is provided in the positive electrode active material layer 25, "the portion of the positive electrode current collector layer 21 that overlaps with the positive electrode active material layer 25 adjacent to the positive electrode current collector layer 21 in the T direction" refers to the portion of the positive electrode current collector layer 21 that overlaps with at least one of the positive electrode active material layer 25 adjacent to the positive electrode current collector layer 21 and the insulating layer 26 provided on the outer periphery of the positive electrode active material layer 25 in the T direction.

[0077] The positive electrode tab 24 is a portion of the positive current collector layer 21 that extends in a specific direction from the main body 22 of the positive current collector layer. For example, the positive electrode tab 24 extends from the main body 22 of the positive current collector layer in the X direction (specifically, the X+ direction). The Y-direction dimension of the positive electrode tab 24 is smaller than the Y-direction dimension of the main body 22 of the positive current collector layer. The shape of the positive electrode tab 24 when viewed along the T direction is, for example, a roughly rectangular shape with its long side extending along the X direction. The front ends of multiple positive electrode tabs 24 are bundled together.

[0078] (Intermediate layer)

[0079] In addition, the all-solid-state battery 1 has, for example, a plurality of intermediate layers 40 disposed between adjacent negative electrode layers 10 and solid electrolyte layers 30.

[0080] The intermediate layer 40 contains, for example, carbon, on which a metal capable of forming an alloy with lithium is supported. Silver is an example of a metal capable of forming an alloy with lithium. The intermediate layer 40 is, for example, a generally rectangular plate with a plate surface extending along the X and Y directions.

[0081] Because the intermediate layer 40 is more flexible than the negative electrode layer 10 and the solid electrolyte layer 30, it is easier to form a tight bond with the negative electrode layer 10 and the solid electrolyte layer 30. The intermediate layer 40 can suppress delamination between the negative electrode layer 10 and the solid electrolyte layer 30.

[0082] (Adhesive layer)

[0083] Here, the all-solid-state battery 1 includes an adhesive layer 50 disposed between an insulating layer 26 and a solid electrolyte layer 30 adjacent to the insulating layer 26.

[0084] The adhesive layer 50 abuts against both the insulating layer 26 and the solid electrolyte layer 30. The adhesive layer 50 is, for example, adhesive. While not particularly limited, the adhesive layer 50 can be, for example, double-sided tape. The adhesive layer 50 can be formed from resin, rubber, etc. The adhesive layer 50 can also be formed from insulating materials such as styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyimide, and ultraviolet (UV) curing resin. The flexibility of the adhesive layer 50 is preferably higher than that of the insulating layer 26. The flexibility of the adhesive layer 50 is preferably higher than that of the solid electrolyte layer 30. This improves the adhesion between the adhesive layer 50 and the insulating layer 26, and between the adhesive layer 50 and the solid electrolyte layer 30.

[0085] The insulating layer 26 has, for example, a first side 27 extending in the Y direction and a second side 28 extending in the X direction. The adhesive layer 50 is preferably provided at least in the first side 27.

[0086] The adhesive layer 50 may be, for example, a flat plate extending along the X and Y directions. The adhesive layer 50 may also be, for example, a strip extending along the Y direction when viewed along the T direction. The adhesive layer 50 may be disposed, for example, on the entire surface of the first edge 27 on the side facing the solid electrolyte layer 30 in the T direction. The adhesive layer 50 may also be disposed, for example, on both of the pair of first edges 27.

[0087] like Figure 6 As shown, the adhesive layer 50 is provided only on the first edge 27 of the insulating layer 26, for example. The adhesive layer 50 is not provided on the second edge 28, for example. The adhesive layer 50 is not provided on the positive electrode active material layer 25.

[0088] Furthermore, a recess 26a, recessed in the T direction, can also be formed in the portion of the insulating layer 26 that overlaps with the adhesive layer 50 in the T direction. The recess depth of the recess 26a (in other words, the T-direction dimension of the recess 26a) is approximately the same as the T-direction dimension of the adhesive layer 50. The surface of the adhesive layer 50 facing each other in the T direction on the side of the solid electrolyte layer 30 is approximately on the same plane as the surface of the positive electrode active material layer 25 facing each other in the T direction on the side of the solid electrolyte layer 30. Therefore, the positive electrode active material layer 25 and the solid electrolyte layer 30 can be brought into contact while the adhesive layer 50 and the solid electrolyte layer 30 are in contact, thus facilitating the migration of electrons between the positive electrode active material layer 25 and the solid electrolyte layer 30.

[0089] The T-direction dimension of the recess 26a is preferably 65% ​​to 100% of the T-direction dimension of the insulating layer 26. The T-direction dimension of the adhesive layer 50 is preferably 5% to 40% of the T-direction dimension of the insulating layer 26. If the T-direction dimension of the insulating layer 26 becomes smaller, the strength of the insulating layer 26 may decrease. If the T-direction dimension of the adhesive layer 50 becomes smaller, the strength of the adhesive layer 50 may decrease. However, with the above structure, the strength of the insulating layer 26 and the adhesive layer 50 can be ensured at the same time.

[0090] (Manufacturing method of all-solid-state batteries)

[0091] Next, use Figure 7 The manufacturing method of the all-solid-state battery 1 according to the embodiment is described. In addition, in this embodiment, the all-solid-state battery 1 using a roll-to-roll production line is described, wherein the roll-to-roll method uses a long strip of positive electrode current collector layer 21 wound into a roll as the positive electrode current collector layer 21.

[0092] First, the positive electrode current collector layer 21 and the positive electrode active material layer 25 are stacked to form the positive electrode layer 20 (positive electrode layer formation step S11). In the positive electrode layer formation step S11, the long strip of positive electrode current collector layer 21, which is wound into a roll, is fed out by a conveying roller, and the positive electrode active material is coated on the conveying positive electrode current collector layer 21 to form the positive electrode active material layer 25. The positive electrode active material layers 25 are formed at intervals according to the design dimensions of the all-solid-state battery 1 after completion. Thus, a positive electrode layer connector with multiple positive electrode active material layers 25 formed at intervals on the long strip of positive electrode current collector layer 21 can be obtained. Next, an insulating layer is formed on the outer periphery of the positive electrode active material layer 25. At this time, an insulating layer 26 is formed on the positive electrode current collector layer 21 on the positive electrode layer 20 according to the design dimensions of the all-solid-state battery 1 after completion. Thus, a positive electrode layer connector with an insulating layer can be obtained. A recess 26a may also be formed in the portion of the insulating layer 26 where the adhesive layer 50 is disposed. Additionally, a positive electrode tab 24 may be formed on the positive current collector layer 21, for example, before the positive current collector layer 21 is wound into a roll. Furthermore, the positive electrode layer formation step is equivalent to a preparation step.

[0093] Next, an adhesive layer 50 is disposed on the insulating layer 26 (adhesive layer disposal step S12). In adhesive layer disposal step S12, for example, adhesive tape that will become adhesive layer 50 is transferred onto the insulating layer 26. The adhesive layer 50 is disposed at least on the first edge 27, for example, only on the first edge 27. Resin or the like that that will become adhesive layer 50 may also be applied to the insulating layer 26.

[0094] Then, the connector of the positive electrode layer 20 with insulating layer 26 is laminated with the strip-shaped solid electrolyte layer 30 (solid electrolyte layer configuration step S13). In solid electrolyte layer configuration step S13, a solid electrolyte layer transfer sheet having solid electrolyte layer 30 can be used, which is peelably laminated onto a strip support sheet. The solid electrolyte layer 30 of the solid electrolyte layer transfer sheet is laminated onto the positive electrode layer 20 of the connector of the positive electrode layer 20 with insulating layer 26 by applying pressure with a transfer roller, and then the strip support sheet is peeled off, thereby transferring the solid electrolyte layer 30. The transfer roller presses the connector of the positive electrode layer 20 with insulating layer 26 and the strip-shaped solid electrolyte layer 30 while feeding them out in the Y direction. An adhesive layer 50 is interposed between the solid electrolyte layer 30 and the insulating layer 26. At this time, the temperature is, for example, room temperature (e.g., 10-35°C), and the pressure is, for example, 50-500 MPa.

[0095] Next, the connector of the positive electrode layer 20 with the insulating layer 26 and the solid electrolyte layer 30 is pressed (positive electrode pressing step S14). The positive electrode layer 20 is made denser through the positive electrode pressing step S14. To make the positive electrode layer 20 denser, the temperature in the positive electrode pressing step S14 is, for example, 25°C to 200°C, and the pressure is, for example, 800 to 1200 MPa. Furthermore, the positive electrode pressing step S14 can improve the adhesion between the adhesive layer 50 and the insulating layer 26, and the adhesion between the adhesive layer 50 and the solid electrolyte layer 30, respectively.

[0096] Next, the stack of the positive electrode layer 20 and the solid electrolyte layer 30 is wound into a roll (positive electrode winding step S15). In the positive electrode winding step S15, the stack is wound into a roll, which is formed by stacking the positive electrode layer 20, on which the insulating layer 26 is provided, and the solid electrolyte layer 30, by interposing an adhesive layer 50 between the insulating layer 26 and the solid electrolyte layer 30.

[0097] On the other hand, a negative electrode layer 10 is formed by depositing a negative electrode active material layer 15 on the negative electrode current collector layer 11 (negative electrode layer placement step S21). In the negative electrode layer placement step S21, the negative electrode current collector layer 11, which is in a wound state, is fed out by a conveying roller, and a negative electrode active material is coated on the negative electrode current collector layer 11 while it is being conveyed. For example, before the negative electrode current collector layer 11 is wound into a roll, a negative electrode tab 14 is formed on the negative electrode current collector layer 11.

[0098] Next, an intermediate layer 40 is disposed on the negative electrode active material layer 15 stacked on the negative electrode current collector layer 11 (intermediate layer disposal step S22). In the intermediate layer disposal step, for example, the intermediate layer 40 is coated onto the negative electrode active material layer 15 while being pressed by a transfer roller, and transfer pressing is performed. At this time, the temperature is, for example, room temperature (e.g., 10 to 35°C), and the pressure is, for example, 50 to 500 MPa.

[0099] Subsequently, the positive electrode layer 20, with the solid electrolyte layer 30 stacked, and the negative electrode layer 10, with the intermediate layer 40 stacked, are stacked together by sandwiching the solid electrolyte layer 20 and the negative electrode layer 10, and then pressed using a pressing device (integration pressing step S31). Thus, through integration pressing, while the negative electrode layer is stacked on the side opposite to the positive electrode layer of the solid electrolyte layer (negative electrode layer arrangement step), the positive electrode layer 20, the negative electrode layer 10, the solid electrolyte layer 30, the intermediate layer 40, and the binder layer 50 are integrated. At this time, the temperature is, for example, 25–100°C, and the pressure is, for example, 500–900 MPa. Through the integration pressing step S31, the positive electrode layer 20, the negative electrode layer 10, the solid electrolyte layer 30, and the binder layer 50 are integrated, thereby increasing the density of the solid electrolyte layer 30.

[0100] In addition, the pressing pressure in the positive electrode pressing step S14 is greater than the pressing pressure in the integrated pressing step S31.

[0101] Next, the formed laminate is cut using a rotary cutter (cutting step S32).

[0102] Next, although not shown, the front ends of multiple negative electrode tabs 14 are bundled together and connected to the negative electrode tab lead 6. The front ends of multiple positive electrode tabs 24 are bundled together and connected to the negative electrode tab lead 6. Next, a resin-coated laminate, which becomes the outer casing 5, is applied. The front ends of the positive electrode tab lead 7 and the negative electrode tab lead 6 are exposed from the outer casing 5.

[0103] Furthermore, the transfer of the solid electrolyte layer 30 to the positive electrode layer 20 in the solid electrolyte layer configuration step S13, the pressing of the positive electrode layer 20 in the positive electrode pressing step S14, the stacking of the negative electrode layer 10 to the positive electrode layer 20 before integration, and the integration pressing in the integration pressing step S31 are performed on both surfaces of the positive electrode layer 20. The transfer of the negative electrode active material layer 15 to the negative electrode current collector layer 11 in the negative electrode layer configuration step S21, and the transfer of the intermediate layer 40 to the negative electrode layer 10 in the intermediate layer configuration step S22, are performed on both surfaces of the negative electrode layer 10. Thus, the all-solid-state battery 1 becomes... Figures 1 to 4 The structure shown is formed by symmetrically stacking the layers on the upper and lower surfaces.

[0104] By following the steps above, you can obtain Figure 1 The all-solid-state battery 1 shown.

[0105] The method for manufacturing the all-solid-state battery 1 according to this embodiment may also include steps other than those described above. The method for manufacturing the all-solid-state battery is not limited to the method described above, and other known methods may also be used.

[0106] (Effects of the implementation method)

[0107] According to the above implementation method, the following effects can be obtained.

[0108] According to the above embodiment, the all-solid-state battery 1 includes an adhesive layer 50, which is disposed between an insulating layer 26 and a solid electrolyte layer 30 adjacent to the insulating layer 26.

[0109] According to the described structure, since the adhesive layer 50 is disposed between the insulating layer 26 and the solid electrolyte layer 30, slippage of the insulating layer 26 relative to the solid electrolyte layer 30 can be suppressed. Therefore, deviation of the positional relationship between the solid electrolyte layer 30 and the positive electrode active material layer 25 from the ideal positional relationship can be suppressed, thereby suppressing the increase in resistance between the solid electrolyte layer 30 and the positive electrode active material layer 25. Thus, an all-solid-state battery 1 with improved battery characteristics can be provided.

[0110] Furthermore, since the deviation in the positional relationship between the solid electrolyte layer 30 and the positive electrode active material layer 25 caused by the repeated expansion and contraction of the all-solid-state battery 1 can be suppressed, the cycle characteristics of the all-solid-state battery 1 can be improved.

[0111] Furthermore, during the manufacturing process of all-solid-state batteries, deviations in the positional relationship between the solid electrolyte layer 30 and the positive electrode active material layer 25 can be suppressed, thereby improving the yield.

[0112] According to the above embodiments, the insulating layer 26 is preferably formed of aluminum oxide.

[0113] According to the structure, since alumina is a material with low conductivity, the insulation performance of the insulating layer 26 can be improved. Therefore, when the negative electrode layer 10 (negative electrode tab 14) is bent and comes into contact with the insulating layer 26, short circuits between the negative electrode layer 10 and the positive electrode layer 20 can be effectively suppressed.

[0114] When the insulating layer 26 is formed of aluminum oxide, it becomes harder, which may cause it to slide easily relative to the solid electrolyte layer 30. However, thanks to the adhesive layer 50, the sliding of the insulating layer 26 relative to the solid electrolyte layer 30 can be suppressed, making it easier to use aluminum oxide as the material for the insulating layer 26.

[0115] According to the above embodiment, the positive electrode active material layer 25 has its length along the X direction. The insulating layer 26 has a first side portion 27 extending along the Y direction. The adhesive layer 50 is preferably disposed between the first side portion 27 and the solid electrolyte layer 30.

[0116] According to the structure described above, slippage of the solid electrolyte layer 30 relative to the insulating layer 26 can be effectively suppressed. Therefore, deviation of the positional relationship between the solid electrolyte layer 30 and the positive electrode layer 20 from the ideal positional relationship can be effectively suppressed.

[0117] According to the above embodiments, the adhesive layer 50 is preferably disposed only between the first side portion 27 and the solid electrolyte layer 30.

[0118] According to the structure, the amount of adhesive layer 50 used can be suppressed while sufficiently suppressing the sliding of the solid electrolyte layer 30 relative to the insulating layer 26.

[0119] In the portion of the insulating layer 26 that overlaps with the adhesive layer 50 in the T direction, a recess 26a that is recessed in the T direction may also be formed.

[0120] According to the structure, the positive electrode active material layer 25 can be easily brought into contact with the solid electrolyte layer 30 while the adhesive layer 50 is in contact with the solid electrolyte layer 30, thereby facilitating the migration of electrons between the positive electrode active material layer 25 and the solid electrolyte layer 30.

[0121] The T-direction dimension of the recess 26a is preferably 65% ​​or more and 100% or less of the T-direction dimension of the insulating layer 26, and more preferably 5% or more and 40% or less of the T-direction dimension of the insulating layer 26.

[0122] If the T-direction dimension of the insulating layer 26 becomes smaller, the strength of the insulating layer 26 may decrease. If the T-direction dimension of the adhesive layer 50 becomes smaller, the strength of the adhesive layer 50 may decrease. However, according to the described structure, the strength of the adhesive layer 50 can be ensured while ensuring the strength of the insulating layer 26.

[0123] According to the above embodiments, the manufacturing method of the all-solid-state battery 1 includes: a positive electrode layer forming step S11, preparing a positive electrode layer with an insulating layer, the positive electrode layer with an insulating layer having a positive electrode layer 20 having a positive electrode active material layer 25 and an insulating layer 26 disposed on the outer periphery of the positive electrode active material layer 25; an adhesive layer placement step S12, placing an adhesive layer 50 on the surface of the insulating layer 26; a solid electrolyte layer placement step S13, stacking a solid electrolyte layer 30 on the surface of the positive electrode layer 20 with the insulating layer 26; and an integrated pressing step S31, stacking a negative electrode layer 10 on the surface of the solid electrolyte layer 30 opposite to the positive electrode layer 20 side.

[0124] According to the manufacturing method, by depositing an insulating layer 26 on the surface of the positive electrode layer 20 to form a positive electrode layer 20, and depositing a solid electrolyte layer 30 on the surface of the positive electrode layer 20 with the insulating layer 26, it is possible to suppress the deviation of the positional relationship between the solid electrolyte layer 30 and the positive electrode active material layer 25 from the ideal positional relationship. This suppresses the increase in resistance between the solid electrolyte layer 30 and the positive electrode active material layer 25, thus providing a manufacturing method for an all-solid-state battery 1 that improves battery characteristics.

[0125] According to the above embodiment, in the adhesive layer configuration step S12, the adhesive layer 50 is configured on the first side portion 27.

[0126] According to the manufacturing method, an all-solid-state battery 1 can be manufactured that can sufficiently suppress the slippage of the solid electrolyte layer 30 relative to the insulating layer 26.

[0127] According to the above embodiment, in the adhesive layer configuration step S12, the adhesive layer 50 is configured only on the first side portion 27.

[0128] According to the manufacturing method, an all-solid-state battery 1 that can sufficiently suppress the slippage of the solid electrolyte layer 30 relative to the insulating layer 26 can be obtained while suppressing the amount of adhesive layer 50 used.

[0129] According to the above embodiments, the manufacturing method of the all-solid-state battery 1 includes a positive electrode winding step S15, in which the positive electrode winding step S15 winds the laminate into a roll. The laminate is formed by stacking a positive electrode layer 20 having an insulating layer 26 and a solid electrolyte layer 30 by interposing an adhesive layer 50 between the insulating layer 26 and the solid electrolyte layer 30.

[0130] According to the manufacturing method described above, an all-solid-state battery 1 can be manufactured efficiently. On the other hand, when multiple all-solid-state batteries are wound into a roll, if the positional relationship between the solid electrolyte layer 30 and the positive electrode layer 20 deviates from the ideal positional relationship, it may be difficult to wind the roll of the solid electrolyte layer 30 and the positive electrode layer 20 into a roll. However, by interposing an adhesive layer 50 between the insulating layer 26 and the solid electrolyte layer 30, the deviation in the positional relationship between the solid electrolyte layer 30 and the positive electrode layer 20 can be suppressed by the adhesive layer 50, thereby making it easier to wind the roll of the solid electrolyte layer 30 and the positive electrode layer 20 into a roll. As a result, the all-solid-state battery 1 can be manufactured more efficiently.

[0131] (Modifications of the implementation method)

[0132] like Figure 8 and Figure 9 As shown, the adhesive layer 50 can also be disposed between the first side 27 and the solid electrolyte layer 30, and between the second side 28 and the solid electrolyte layer 30. Furthermore, in this specification, the adhesive layer 50 disposed on the first side 27 is sometimes referred to as "adhesive layer 50a". The adhesive layer 50 disposed on the second side 28 is sometimes referred to as "adhesive layer 50b".

[0133] According to the structure described, the slippage of the solid electrolyte layer 30 relative to the insulating layer 26 can be more effectively suppressed.

[0134] For example, the adhesive layer 50b disposed on the second side 28 may also be disposed only in a portion of the region between the second side 28 and the solid electrolyte layer 30 in the X direction (see reference). Figure 8 The adhesive layer 50b disposed between the second side 28 and the solid electrolyte layer 30 may, for example, be disposed separately from each of the first sides 27, specifically disposed in the central part in the X direction of the region between the second side 28 and the solid electrolyte layer 30.

[0135] The adhesive layer 50b may be disposed in the region between the second edge 28 and the solid electrolyte layer 30, or it may be disposed in the entire region between the second edge 28 and the solid electrolyte layer 30 (see reference). Figure 9 The adhesive layer 50 may also be disposed over the entire area between the insulating layer 26 and the solid electrolyte layer 30. In adhesive layer configuration step S12, the adhesive layer 50 may also be disposed over the second edge 28.

[0136] According to the structure described, the slippage of the solid electrolyte layer 30 relative to the insulating layer 26 can be more effectively suppressed.

[0137] Furthermore, there are no particular restrictions on the range of the adhesive layer 50a provided in the first side portion 27, as long as it can sufficiently suppress the deviation between the solid electrolyte layer 30 and the positive electrode layer 20.

[0138] Furthermore, the adhesive layer 50 can also be separated from the outer periphery of the insulating layer 26. In this case, when the negative electrode tab 14 bends, the insulating layer 26 can be used to suppress contact between the negative electrode tab 14 and the adhesive layer 50. Preferably, the adhesive layer 50 is separated from the positive electrode active material layer 25.

[0139] like Figure 10 As shown, the adhesive layer 50 can also be in the form of dots (in other words, granules).

[0140] According to the structure, the amount of adhesive layer 50 used can be suppressed while sufficiently suppressing the sliding of the solid electrolyte layer 30 relative to the insulating layer 26.

[0141] Multiple dot-shaped adhesive layers 50 are provided on the insulating layer 26. Preferably, the dot-shaped adhesive layers 50 are provided at least on the first edge 27.

[0142] In the above embodiments and variations, the adhesive layer 50 is disposed in at least the region between the first edge 27 and the solid electrolyte layer 30, within the area between the insulating layer 26 and the solid electrolyte layer 30. However, the adhesive layer 50 may also be disposed only in the region between the second edge 28 and the solid electrolyte layer 30, within the area between the insulating layer 26 and the solid electrolyte layer 30. However, by disposing the adhesive layer 50 in the region between the first edge 27 and the solid electrolyte layer 30, the sliding of the solid electrolyte layer 30 relative to the insulating layer 26 can be more effectively suppressed.

[0143] In the above embodiments and variations, the insulating layer 26 is rectangular, but is not limited to this. For example, the insulating layer may not have a second side. The insulating layer may also be provided along the X-direction edge of the positive electrode active material layer 25, forming a strip with the Y-direction as its length direction. With such an insulating layer, the generation of short circuits caused by contact between the positive electrode layer 20 and the negative electrode tab 14 can also be suppressed.

[0144] This invention is not limited to the configurations described above, and can be appropriately modified and applied without changing the spirit of the invention. Furthermore, combinations of two or more of the preferred configurations described in the above embodiments also fall under this invention.

[0145] Figure Labels

[0146] 1: All-solid-state batteries

[0147] 20: Positive electrode layer

[0148] 21: Positive current collector layer

[0149] 24: Positive electrode tab

[0150] 25: Positive electrode active material layer

[0151] 26: Insulation layer

[0152] 27: First side

[0153] 28: Second side

[0154] 30: Solid electrolyte layer

[0155] 50: Adhesive layer

[0156] S15: Positive electrode winding step.

Claims

1. A solid-state battery, comprising stacking a negative electrode layer and a positive electrode layer having a positive electrode active material layer in between, separated by a solid electrolyte layer. An insulating layer is provided on the outer periphery of the aforementioned positive electrode active material layer, and It has an adhesive layer disposed between the aforementioned insulating layer and the aforementioned solid electrolyte layer adjacent to the insulating layer.

2. The all-solid-state battery according to claim 1, wherein, The aforementioned insulating layer is formed of aluminum oxide.

3. The all-solid-state battery according to claim 1, wherein, When the direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked, separated by the aforementioned solid electrolyte layer, is defined as the stacking direction, one of the directions orthogonal to the aforementioned stacking direction is defined as the first direction, and the direction orthogonal to both the aforementioned stacking direction and the aforementioned first direction is defined as the second direction, The aforementioned positive electrode active material layer has its length along the aforementioned first direction. The aforementioned insulating layer has a first edge extending along the aforementioned second direction. The aforementioned adhesive layer is disposed between the aforementioned first edge and the aforementioned solid electrolyte layer.

4. The all-solid-state battery according to claim 3, wherein, The aforementioned adhesive layer is disposed only between the aforementioned first edge and the aforementioned solid electrolyte layer.

5. The all-solid-state battery according to claim 3, wherein, The aforementioned insulating layer has a second side portion, which is adjacent to and extends along the aforementioned first side portion in the aforementioned first direction. The aforementioned adhesive layer is disposed between the aforementioned second side and the aforementioned solid electrolyte layer.

6. The all-solid-state battery according to claim 1, wherein, The aforementioned adhesive layer is dotted.

7. The all-solid-state battery according to claim 1, wherein, The direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked, separated by the aforementioned solid electrolyte layer, is defined as the stacking direction. In the aforementioned insulating layer, the portion that overlaps with the aforementioned adhesive layer in the aforementioned stacking direction is formed with a recess that is recessed in the aforementioned stacking direction.

8. The all-solid-state battery according to claim 7, wherein, The aforementioned dimension of the aforementioned recess in the stacking direction is 65% or more and 100% or less of the aforementioned dimension of the aforementioned insulating layer in the stacking direction.

9. A method for manufacturing an all-solid-state battery, comprising manufacturing the all-solid-state battery according to claim 1, the method comprising: Preparation steps: Prepare a positive electrode layer with an insulating layer. The positive electrode layer with an insulating layer has a positive electrode active material layer and an insulating layer disposed on the outer periphery of the positive electrode active material layer. The adhesive layer preparation step involves preparing an adhesive layer on the surface of the aforementioned insulating layer; The solid electrolyte layer configuration step involves stacking a solid electrolyte layer on the surface of the aforementioned insulating positive electrode layer; and, The negative electrode layer configuration step involves stacking a negative electrode layer on the opposite side of the aforementioned solid electrolyte layer to the aforementioned positive electrode layer.

10. The method for manufacturing an all-solid-state battery according to claim 9, wherein, In the aforementioned solid electrolyte layer configuration step, the direction in which the aforementioned negative electrode layer and the aforementioned positive electrode layer are stacked with respect to the aforementioned solid electrolyte layer is defined as the stacking direction. One of the directions orthogonal to the aforementioned stacking direction is defined as the first direction, and the direction orthogonal to both the aforementioned stacking direction and the aforementioned first direction is defined as the second direction. In the aforementioned preparation steps, a positive electrode active material layer with the first direction set as the length direction and an insulating layer having a first edge extending along the second direction are formed. In the aforementioned adhesive layer configuration step, the aforementioned adhesive layer is configured on the aforementioned first edge.

11. The method for manufacturing an all-solid-state battery according to claim 10, wherein, In the aforementioned adhesive layer configuration step, the adhesive layer is configured only on the aforementioned first edge.

12. The method for manufacturing an all-solid-state battery according to claim 10, wherein, In the aforementioned preparation steps, a positive electrode layer with an insulating layer is prepared. This insulating layer further has a second side portion that is adjacent to and extends along the first direction from the first side portion. In the aforementioned adhesive layer configuration step, the aforementioned adhesive layer is configured on the aforementioned second side.

13. The method for manufacturing an all-solid-state battery according to claim 9, wherein, The device includes a positive electrode winding step, wherein the positive electrode winding step winds the laminate into a roll, and the laminate is formed by stacking the aforementioned positive electrode layer, on which the aforementioned insulating layer is disposed, and the aforementioned solid electrolyte layer, by interposing the aforementioned adhesive layer between the aforementioned insulating layer and the aforementioned solid electrolyte layer.

14. The method for manufacturing an all-solid-state battery according to claim 9, wherein, This further includes the step of disposing an intermediate layer between the aforementioned negative electrode layer and the aforementioned solid electrolyte layer.

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