JP7040331B2 - Manufacturing method of series-stacked all-solid-state battery - Google Patents

Description

The present disclosure relates to a method for manufacturing a series laminated all-solid-state battery.

In recent years, with the rapid spread of information-related devices such as personal computers, video cameras, and mobile phones, and communication devices, the development of stacked batteries used as a power source thereof has been regarded as important. Further, in the automobile industry and the like, the development of high-output and high-capacity laminated all-solid-state batteries for electric vehicles or hybrid vehicles is being promoted.

For example, in Patent Document 1, the housing accommodating the charging / discharging portion has a positioning convex portion, the component of the charging / discharging portion has a hole into which the positioning convex portion can be inserted, and the charging / discharging portion is charged / discharged along the positioning convex portion. A method for manufacturing an all-solid-state battery including a laminating step of laminating component components is disclosed.

Further, in Patent Document 2, an electrode body held by a support structure having a clip mechanism is placed on a pedestal, and each electrode is laminated from a direction perpendicular to the plane direction of the bipolar electrode, and the clip mechanism is formed. A method for manufacturing a bipolar battery including a step of eliminating the problem is disclosed.

In addition, Patent Document 3 discloses a fuel cell stack in which unit batteries are stacked by using a positioning guide.

Japanese Unexamined Patent Publication No. 2011-103279 Japanese Unexamined Patent Publication No. 2012-190809 Japanese Patent Application Laid-Open No. 2003-086232

The laminated all-solid-state battery, in which the electrolyte is replaced with a solid electrolyte layer and the battery is completely solidified, does not use a flammable organic solvent in the battery, which simplifies the safety device and reduces the manufacturing cost. It is attracting attention because of its excellent productivity.

When manufacturing such a laminated all-solid-state battery, usually, a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated to form a unit battery. To form. Then, the unit batteries are stacked in series or in parallel to form a battery laminate. After that, an all-solid-state battery is manufactured by connecting the battery laminate to the electrode terminals and accommodating the battery laminate in an exterior body or the like.

However, when the battery laminate is accommodated from the opening of the exterior body, the positive electrode current collector layer, the positive electrode active material layer, the solid electrolyte layer, the negative electrode active material layer, or the negative electrode current collector layer contained in the battery laminate is used. Material may fall off from the edges. In particular, as the distance for moving the battery laminate in the direction perpendicular to the plane direction becomes longer in the exterior body, the contact between the inner wall of the exterior body and the end portion of the battery laminate causes the battery laminate to come into contact with each other. The material from the edges is likely to fall off. When the material is shed in this way, the shed material may adhere to the ends of the other layers, resulting in a short circuit.

Therefore, the present disclosure has been made in view of the above circumstances, and is a series-stacked all-solid-state battery capable of suppressing the material from falling off from the end portion of the battery laminate when the battery laminate is housed in the exterior body. The purpose is to provide a manufacturing method.

The present inventor of the present disclosure has found that the above-mentioned problems can be solved by a method for manufacturing a series-stacked all-solid-state battery including the following steps:
(A) Preparing an exterior body having an accommodating portion for accommodating the battery laminate, wherein the exterior body has through holes at both ends and is divided in the stacking direction of the battery laminate. The battery laminate is composed of two or more unit batteries stacked in series, and the unit battery includes a positive electrode current collector layer and a positive electrode active material layer. , A solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated in this order;
(B) The unit battery or one or a plurality of layers constituting the unit battery are inserted into the accommodating portion of one partial exterior body in order from within ± 60 ° in a direction perpendicular to the stacking direction. matter;
(C) All the partial exterior bodies are combined to form the exterior body, whereby the battery laminate is housed in the exterior body;
(D) The electrode terminals are connected to both end faces in the stacking direction of the battery laminate through the through holes at both ends of the exterior body.

According to the method for manufacturing a series-stacked all-solid-state battery of the present disclosure, it is possible to prevent the material from falling off from the end portion of the battery laminate when the battery laminate is housed in the exterior body.

FIG. 1 is a schematic cross-sectional view showing one form of each step included in the method for manufacturing a series-stacked all-solid-state battery of the present disclosure. FIG. 2 is a schematic view showing one form in which the pressing process is included in the middle of the process (d).

Hereinafter, embodiments for carrying out the present disclosure will be described in detail with reference to the drawings. For convenience of explanation, the same reference numerals are given to the same or corresponding parts in each figure, and duplicate explanations will be omitted. Not all of the components of the embodiment are essential, and some components may be omitted. However, the form shown in the figure below is an example of the present disclosure and does not limit the present disclosure.

<< Manufacturing method of series-stacked all-solid-state battery >>
The method for manufacturing a series laminated all-solid-state battery of the present disclosure includes the following steps:
(A) Preparing an exterior body having an accommodating portion for accommodating the battery laminate, wherein the exterior body has through holes at both ends and is divided in the stacking direction of the battery laminate. The battery laminate is composed of at least two partial exterior bodies having a shape, and two or more unit batteries are laminated in series, and the unit battery is a positive electrode current collector layer, a positive electrode active material layer, and a solid electrolyte layer. , The negative electrode active material layer, and the negative electrode current collector layer are laminated in this order;
(B) Insert the unit battery or one or more layers constituting the unit battery in order with respect to the accommodating portion of one partial exterior body from within ± 60 ° in the direction perpendicular to the stacking direction;
(C) All the partial exterior bodies are combined to form an exterior body, whereby the battery laminate is housed in the exterior body;
(D) Connect the electrode terminals to both end faces of the battery laminate in the stacking direction through the through holes at both ends of the exterior body.

In the present disclosure, the "series laminated all-solid-state battery" is an all-solid-state battery having a battery laminate in which two or more unit batteries are laminated in series, and is located at both end faces in the stacking direction of the battery laminate. It is an all-solid-state battery that can be charged and discharged from the current collector layer. Examples of series-stacked all-solid-state batteries include, but are not limited to, bipolar all-solid-state batteries.

The "stacking direction of the battery laminate" is the direction in which the unit batteries constituting the battery laminate or the layers constituting the unit battery are laminated, that is, the plane direction of the unit battery or each layer constituting the unit battery. Points in the axial direction perpendicular to. In the case where the exterior body has not yet accommodated the battery laminate, it refers to the stacking direction of the battery laminate to be accommodated by the exterior body.

<Step (a)>
In the step (a), an exterior body having an accommodating portion for accommodating the battery laminate is prepared.

Here, in the stacking direction of the battery laminate, the exterior body is composed of at least two partial exterior bodies having through holes at both ends and having a divided shape, and the battery laminate is a unit battery. Two or more are laminated in series, and the unit battery is configured by laminating a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer in this order. There is.

For example, FIG. 1A is a schematic cross-sectional view showing an embodiment in which an exterior body 11 having an accommodating portion 11a for accommodating a battery laminate 10 is prepared. Here, in the stacking direction of the battery laminated body 10, the exterior body 11 has through-hole portions 11b and 11c at both ends. Further, the exterior body 11 is composed of two partial exterior bodies 11x and 11y having a divided shape. Since the details of the battery laminate 10 are shown in the right figure of FIG. 1 (b), the description thereof will be omitted here.

The shape of the exterior body is not particularly limited, and can be appropriately set according to the shape of the battery laminate to be accommodated. For example, when the battery laminate is a cylinder, the exterior body may be a cylinder having a size capable of accommodating the battery laminate.

The accommodating portion in the exterior body is a space for accommodating the battery laminate. Therefore, if the battery laminate can be accommodated after all the partial exterior bodies having the divided shapes are combined, even if any one partial exterior body having the divided shape has the accommodating portion. Well, it doesn't have to be.

The number of partial exterior bodies constituting the exterior body is not particularly limited as long as it is two or more, that is, the exterior body is divided into two, three, four, or the like in the stacking direction of the battery laminate. Although it may consist of a partial exterior body having a different shape, it is preferably composed of a partial exterior body having a shape divided into two from the viewpoint of operability. Further, the shape (or size) of each partial exterior body is not particularly limited, and may be the same or different.

Further, in the stacking direction of the battery laminate, the exterior body has through holes at both ends. The through-hole portion is an opening for connecting the electrode terminals to both end faces in the stacking direction of the battery laminate, which will be described later. For example, as shown in FIG. 1A, the exterior body 11 has through-hole portions 11b and 11c at both ends in the stacking direction of the battery laminated body. In the step (d) described later, the electrode terminals 31 and 30 can be connected to both end faces of the battery laminate 10 in the stacking direction through the through-hole portions 11b.

The sizes of the through holes at both ends of the exterior body may be the same or different from each other. The upper limit of each size may be the same as the area in the surface direction of the inner surface of the exterior body, and the lower limit of each size may be such that the electrode terminals can be connected.

The size of the through-hole portion of the exterior body is, for example, 100% or less, 95% or less, 90% or less, 85% or less, 80% or less, 75% or less, 70% or less of the area of the end face of the battery laminate. It may be 65% or less, 60% or less, 55% or less, 50% or less, 40% or less, or 30% or less.

When the battery laminate is pressed inside the exterior, which will be described later, the battery laminate can be pressed through the through hole portion of the exterior. Further, from the viewpoint of operability when the step of pressing the battery laminate is included, the size of the through hole portion of the exterior body on the side where the battery laminate comes into contact with the pressing means is in contact with the pressing means of the battery laminate. It is preferable that the size of the end face on the side to be used is the same.

The material constituting the exterior body is not particularly limited, and may be, for example, metal or fiber reinforced plastic. As the metal, for example, a material having appropriate rigidity such as aluminum, an aluminum alloy, and stainless steel is used, but the metal is not limited thereto. Examples of the fiber reinforced plastic include, but are not limited to, carbon fiber reinforced plastic, boron fiber reinforced plastic, aramid fiber reinforced plastic, polyethylene fiber reinforced plastic, and Zylon reinforced plastic.

The exterior body may further have an insulating layer on its inner wall. The insulating layer is not particularly limited, and may be, for example, an insulating film layer or an insulating resin layer. In particular, when a metal is used as the exterior body, a mode in which the inner wall of the exterior body further has an insulating layer is preferable because a short circuit between the exterior body and the current collector layer can be prevented. It is also possible to prevent a short circuit by performing an insulating treatment on the end of each layer of the battery laminate instead of the insulating layer.

<Step (b)>
In the step (b), the unit battery or one or a plurality of layers constituting the unit battery are sequentially inserted into the accommodating portion of one partial exterior body from within ± 60 ° in the direction perpendicular to the stacking direction.

As in step (b), the unit battery or one or more layers constituting the unit battery are inserted in order from within ± 60 ° in the direction perpendicular to the stacking direction with respect to the accommodating portion of one partial exterior body. By doing so, the partial exterior body can directly serve as a guide for the unit battery or one or a plurality of layers constituting the unit battery, and facilitate the alignment of each layer constituting the unit battery (or the battery laminate). This makes it possible to prevent misalignment of each layer.

Further, the unit battery or one or a plurality of layers constituting the unit battery are sequentially arranged within a direction of ± 45 ° perpendicular to the stacking direction and within a direction of ± 30 ° with respect to the accommodating portion of one partial exterior body. It may be inserted from within ± 15 ° and from ± 0 ° (that is, in the direction perpendicular to the stacking direction), preferably from ± 0 ° in the direction perpendicular to the stacking direction (that is, in the direction perpendicular to the stacking direction). insert.

For example, FIG. 1B is a schematic cross-sectional view showing one form of step (b). As shown in the left figure of FIG. 1 (b), the layers constituting the unit battery 6c: positive electrode / negative electrode current collector layer 5c, positive electrode active material layer 4c, 5c, 4c, ... It is inserted from the direction perpendicular to the stacking direction of the battery laminated body 10 with respect to the accommodating portion of 11x. As a result, as shown in the right figure of FIG. 1 (b), the battery laminate 10 formed by laminating the unit batteries 6a, 6b, and 6c in series is inserted into the accommodating portion of the partial exterior body 11x. There is.

Further, the active material layer and the solid electrolyte layer constituting the unit battery can be formed by powder forming (press forming) each constituent material.

For example, a positive electrode is formed by compacting a constituent material containing a positive electrode active material and an additive used for the positive electrode active material layer of an all-solid-state battery such as a solid electrolyte, a conductive auxiliary agent, and a binder, which are used as needed. An active material layer can be formed. Further, a negative electrode is formed by powder molding a constituent material containing a negative electrode active material and an additive used for the negative electrode active material layer of an all-solid-state battery such as a solid electrolyte, a conductive auxiliary agent, and a binder, which are used as needed. An active material layer can be formed. Further, a solid electrolyte layer is formed by powder molding a constituent material containing a solid electrolyte and additives used for the solid electrolyte layer of an all-solid-state battery such as a conductive auxiliary agent and a binder used as needed. Can be done.
<Step (c)>
In the step (c), all the partial exterior bodies are combined to form the exterior body, whereby the battery laminate is housed in the exterior body.

For example, FIG. 1 (c) is a schematic cross-sectional view showing one form of step (c). As shown in FIG. 1 (c), in order to accommodate the battery laminate 10 arranged in the accommodating portion of the partial exterior body 11x, the partial exterior body 11x and the other partial exterior body 11y are coupled to each other. , The exterior body 11 is formed, whereby the battery laminate 10 is housed in the exterior body 11.

<Step (d)>
In the step (d), the electrode terminals are connected to both end faces in the stacking direction of the battery laminate through the through holes at both ends of the exterior body.

By connecting the electrode terminals, the electric power generated by the battery laminate can be taken out to the outside.

For example, FIG. 1D shows a form in which the electrode terminals 30 and 31 are connected to both end faces of the battery laminate 10 in the stacking direction through through holes 11c and 11b at both ends of the exterior body.

Further, as the electrode terminal, one having a function as a current collector layer can be used. In this case, it is not the current collector layer but the positive electrode active material layer or the negative electrode active material layer that is located at the end face in the stacking direction of the battery laminate, and these active material layers function as the current collector layer. You may connect the electrode terminal which also has.

Further, it is preferable to further include a pressing step before, during, or after the step (d). The pressing step is a step of pressing the battery laminate in the stacking direction of the battery laminate.

For example, FIG. 2 is a schematic view showing one form in which this pressing process is included in the middle of the process (d). As shown in FIG. 2A, the electrode terminal 32 is connected to the lower end surface of the battery laminate 20 in the stacking direction. After that, as shown in FIG. 2B, the battery laminate 20 is pressed along the stacking direction of the battery laminate 20 and toward the end face to which the electrode terminals 32 are connected. Then, as shown in FIG. 2C, the electrode terminal 33 is connected to the upper end surface of the battery laminate 20 in the stacking direction. In this way, by performing the pressing step in the middle of the step (d), the battery laminate 20 can be constrained in the stacking direction. The exterior body 21 has an insulating layer 22 on its inner wall.

As described above, according to the method of the present disclosure, it is possible to manufacture a series-stacked all-solid-state battery capable of suppressing the material from falling off during manufacturing.

<< Series-stacked all-solid-state battery >>

The all-solid-state battery of the present disclosure manufactured by the above-mentioned method has a battery laminate in which two or more unit batteries are laminated in series.

Here, the unit battery is configured by laminating a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer in this order.

For example, the battery laminate 10 shown on the right side of FIG. 1B is formed by laminating three unit batteries 6a, 6b, and 6c in series. Further, the unit battery 6a is configured by laminating a positive electrode / negative electrode current collector layer 1a, a negative electrode active material layer 2a, a solid electrolyte layer 3a, a positive electrode active material layer 4a, and a positive electrode / negative electrode current collector layer 5a in this order. Has been done. The unit battery 6b is configured by laminating a positive electrode / negative electrode current collector layer 1b, a negative electrode active material layer 2b, a solid electrolyte layer 3b, a positive electrode active material layer 4b, and a positive electrode / negative electrode current collector layer 5b in this order. There is. The unit battery 6c is configured by laminating a positive electrode / negative electrode current collector layer 1c, a negative electrode active material layer 2c, a solid electrolyte layer 3c, a positive electrode active material layer 4c, and a positive electrode / negative electrode current collector layer 5c in this order. There is.

When two or more unit batteries are stacked in series, the two unit batteries adjacent to each other in the stacking direction may share a positive electrode / negative electrode current collector layer used as both a positive electrode and a negative electrode current collector layer.

That is, in the stacking direction, the battery laminate has a negative electrode current collector layer (or positive electrode / negative electrode current collector layer), a negative electrode active material layer, a solid electrolyte layer, a positive electrode active material layer, a positive electrode / negative electrode current collector layer, and a negative electrode. The active material layer, the solid electrolyte layer, the positive electrode active material layer, and the positive electrode current collector layer (or the positive electrode / negative electrode current collector layer) can be laminated in this order to form a battery laminate. In this case, since the "positive electrode / negative electrode current collector layer" is used as both the positive electrode and the negative electrode current collector layer, either the "positive electrode current collector layer" or the "negative electrode current collector layer" referred to in the present disclosure. Also applies.

For example, as shown in the right figure of FIG. 1 (b), the unit battery 6a and the unit battery 6b share the positive electrode / negative electrode current collector layer 5a (1b), and the unit battery 6b and the unit battery 6c shares the positive electrode / negative electrode current collector layer 5b (1c).

It is not necessary to share such a positive electrode / negative electrode current collector between the unit batteries, and in that case, a positive electrode current collector layer and a negative electrode current collector layer are provided in accordance with the adjacent active material layer. , These can be brought into electrical contact with each other (not shown).

In the present disclosure, the battery laminate can be constrained in the stacking direction. Thereby, during charging / discharging, the conductivity of ions and electrons can be improved inside each layer of the all-solid-state battery laminate and between each layer, and the battery reaction can be further promoted.

The shape of the battery laminate is not particularly limited, and may be, for example, a coin type, a laminated type, a cylindrical type, a square type, or the like.

Specific examples of the constituent materials of each layer constituting the unit battery will be described as follows. In order to easily understand the present disclosure, a unit battery used for the all-solid-state lithium-ion secondary battery will be described as an example, but the all-solid-state battery of the present disclosure is not limited to the lithium-ion secondary battery and is widely used. Applicable.

(Positive current collector layer)
The conductive material used for the positive electrode current collector layer is not particularly limited, and any material that can be used for an all-solid-state battery can be appropriately adopted. For example, the conductive material used for the positive electrode current collector layer may be, but is not limited to, SUS, aluminum, copper, nickel, iron, titanium, carbon, or the like.

The shape of the positive electrode current collector layer is not particularly limited, and examples thereof include a foil shape, a plate shape, and a mesh shape. Of these, foil-like is preferable.

(Positive electrode active material layer)
The positive electrode active material layer contains at least a positive electrode active material, and preferably further contains a solid electrolyte described later. In addition, an additive used for the positive electrode active material layer of an all-solid-state battery such as a conductive auxiliary agent or a binder can be included according to the intended use and purpose of use.

The material of the positive electrode active material is not particularly limited. For example, the positive electrode active material is lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), LiCo _1/3 Ni _1/3 Mn _1/3 O ₂ , Li _{1 + x.} Different element substitution Li-Mn spinel having a composition represented by Mn _{2- xy My} O ₄ (M is one or more metal elements selected from Al, Mg, Co, Fe, Ni, and Zn) and the like. However, it is not limited to these.

The conductive auxiliary agent is not particularly limited. For example, the conductive auxiliary agent may be, but is not limited to, a carbon material such as VGCF (vapor grown carbon fiber) and carbon nanofibers, and a metal material.

The binder is not particularly limited. For example, the binder may be, but is not limited to, a material such as polyvinylidene fluoride (PVdF), carboxymethyl cellulose (CMC), butadiene rubber (BR) or styrene butadiene rubber (SBR), or a combination thereof.

(Solid electrolyte layer)
The solid electrolyte layer contains at least a solid electrolyte. The solid electrolyte is not particularly limited, and a material that can be used as a solid electrolyte for an all-solid-state battery can be used. For example, the solid electrolyte may be, but is not limited to, a sulfide solid electrolyte, an oxide solid electrolyte, a polymer electrolyte, or the like.

Examples of the sulfide solid electrolyte include, but are not limited to, a sulfide-based amorphous solid electrolyte, a sulfide-based crystalline solid electrolyte, and an argylodite-type solid electrolyte. As specific examples of sulfide solid electrolytes, Li ₂ SP ₂ S ₅ series (Li ₇ P ₃ S ₁₁ , Li ₃ PS ₄ , Li ₈ P ₂ S ₉ , etc.), Li ₂ S-SiS ₂ , Li I -Li ₂ S-SiS ₂ , LiI-Li ₂ SP ₂ S ₅ , LiI-LiBr-Li ₂ SP ₂ S ₅ , Li ₂ SP ₂ S ₅ -GeS ₂ (Li ₁₃ GeP ₃ S ₁₆ ) , Li ₁₀ GeP ₂ S ₁₂ , etc.), LiI-Li ₂ SP ₂ O ₅ , LiI-Li ₃ PO ₄ -P ₂ S ₅ , Li _7-x PS _6-x Cl _x , etc .; or a combination thereof. It can be mentioned, but is not limited to these.

Examples of solid oxide electrolytes are Li ₇ La ₃ Zr ₂ O _12, Li _7-x La ₃ Zr _1-x Nb _x O _12, Li _7-3 x La ₃ Zr ₂ Al _x O ₁₂ , Li _{3 x} La _{2 / 3-x} TiO ₃ , Li _{1 + x} Al _x Ti _2-x (PO ₄ ) ₃ , Li _{1 + x} Al _x Ge _2-x (PO ₄ ) ₃ , Li ₃ PO ₄ or Li _{3 + x} PO _4-x N _x (LiPON ), Etc., but are not limited to these.

(Polymer electrolyte)
Examples of the polymer electrolyte include, but are not limited to, polyethylene oxide (PEO), polypropylene oxide (PPO), and copolymers thereof.

The solid electrolyte may be glass or crystallized glass (glass ceramic). Further, the solid electrolyte layer may contain a binder or the like, if necessary, in addition to the above-mentioned solid electrolyte. As a specific example, it is the same as the "binder" listed in the above-mentioned "positive electrode active material layer", and the description thereof is omitted here.

(Negative electrode active material layer)
The negative electrode active material layer contains at least the negative electrode active material, and preferably further contains the above-mentioned solid electrolyte. In addition, an additive used for the negative electrode active material layer of an all-solid-state battery such as a conductive auxiliary agent or a binder can be included according to the intended use and purpose of use.

The material of the negative electrode active material is not particularly limited, and it is preferable that metal ions such as lithium ions can be occluded and released. For example, the negative electrode active material may be an alloy-based negative electrode active material, a carbon material, or the like, but is not limited thereto.

The alloy-based negative electrode active material is not particularly limited, and examples thereof include a Si alloy-based negative electrode active material and a Sn alloy-based negative electrode active material. Examples of the Si alloy-based negative electrode active material include silicon, silicon oxide, silicon carbide, silicon nitride, and a solid solution thereof. Further, the Si alloy-based negative electrode active material may contain elements other than silicon, for example, Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Sn, Ti and the like. Sn alloy-based negative electrode active materials include tin, tin oxide, tin nitride, and solid solutions thereof. Further, the Sn alloy-based negative electrode active material may contain elements other than tin, for example, Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Ti, Si and the like. Among these, a Si alloy-based negative electrode active material is preferable.

The carbon material is not particularly limited, and examples thereof include hard carbon, soft carbon, graphite, and the like.

As the solid electrolyte, the conductive auxiliary agent, the binder and other additives used for the negative electrode active material layer, those described in the above-mentioned "Positive electrode active material layer" and "Solid electrolyte layer" can be appropriately adopted. ..

(Negative electrode current collector layer)
The conductive material used for the negative electrode current collector layer is not particularly limited, and any material that can be used for an all-solid-state battery can be appropriately adopted. For example, the conductive material used for the negative electrode current collector layer may be, but is not limited to, SUS, aluminum, copper, nickel, iron, titanium, carbon, or the like.

The shape of the negative electrode current collector layer is not particularly limited, and examples thereof include a foil shape, a plate shape, and a mesh shape. Of these, foil-like is preferable.

The size of the negative electrode active material layer may be the same as or different from the size of the positive electrode active material layer, but the metal ions released from the positive electrode active material layer during charging are used as the negative electrode active material layer. From the viewpoint of reliable and smooth movement, the size of the negative electrode active material layer is preferably set to be larger than the size of the positive electrode active material layer.

Further, the size of the positive electrode current collector layer, the negative electrode current collector layer, or the positive electrode / negative electrode current collector layer may be set to be the same as the size of the solid electrolyte layer (not shown).

1a, 5a, 1b, 5b, 1c, 5c Positive electrode / negative electrode current collector layer 2a, 2b, 2c, 2d, 2e Negative electrode active material layer 3a, 3b, 3c, 3d, 3e Solid electrolyte layer 4a, 4b, 4c, 4d 4e Positive electrode active material layer 6a, 6b, 6c Unit battery 10, 20 Battery laminate 11, 21 Exterior 11a Exterior housing 11x, 11y Partial exterior 11b, 11c Through hole 22 Insulation layer 30, 31, 32 , 33 Electrode terminal

Claims (1)

Manufacturing method of series laminated all-solid-state battery including the following steps:
(A) Preparing an exterior body having an accommodating portion for accommodating the battery laminate, wherein the exterior body has through holes at both ends and is divided in the stacking direction of the battery laminate. The battery laminate is composed of two or more unit batteries stacked in series, and the unit battery includes a positive electrode current collector layer and a positive electrode active material layer. , A solid electrolyte layer, a negative electrode active material layer, and a negative electrode current collector layer are laminated in this order;
(B) With respect to the accommodating portion of one of the at least two partial exterior bodies in a state in which the unit battery or one or a plurality of layers constituting the unit battery are sequentially divided. , Insert from within ± 60 ° in the direction perpendicular to the stacking direction;
(C) All the partial exterior bodies are combined to form the exterior body, whereby the battery laminate is housed in the exterior body;
(D) The electrode terminals are connected to both end faces in the stacking direction of the battery laminate through the through holes at both ends of the exterior body.

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