JP7067455B2 - 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, a plurality of unit batteries having 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 bipolar type or monopolar type. A method for manufacturing a connected laminated all-solid-state battery is disclosed.

Patent Document 2 has a laminated body in which a positive electrode and a negative electrode are laminated via a separator, and a part of the peripheral portion of the separator of the laminated body is adhered to each other to be firmly integrated, and the outer peripheral portion of the laminated body is formed. A liquid-based laminated battery in which a heat-shrinkable film is arranged so as to surround the battery is disclosed.

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

Japanese Unexamined Patent Publication No. 2016-136490 Japanese Patent Application Laid-Open No. 2002-208442 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 manufacturing costs and production. It is attracting attention because of its excellent sex.

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) to (e):
(A) Holds a semi-cylindrical cartridge for accommodating a battery laminate, a tubular exterior body for accommodating the battery laminate and the semi-cylindrical cartridge, and the semi-cylindrical cartridge and the tubular exterior body. Provided to provide a holder for the above, wherein the battery laminate has two or more unit batteries connected in series, wherein the unit battery is a positive electrode collector layer, a positive electrode active material. The layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer are laminated in this order, and one end of the tubular exterior body is an open end portion;
(B) The unit battery or the unit battery is placed in the semi-cylindrical cartridge which holds the semi-cylindrical cartridge in the holder in an oblique state and is held in the holder in an oblique state. To form the battery laminate by sequentially stacking one or a plurality of layers constituting the above, thereby accommodating the battery laminate in the semi-cylindrical cartridge;
(C) The semi-cylindrical cartridge and the battery laminate are arranged so that the shaft of the battery laminate and the axis of the tubular exterior body are aligned in a straight line, and the shaft of the semi-cylindrical cartridge and the battery laminate are passed through the lower opening end of the tubular exterior body. Is inserted into the tubular exterior body in an oblique state;
(D) The semi-cylindrical cartridge and the battery laminate are housed in a state where the tubular exterior body is held by the holder or after the tubular exterior body is removed from the holder. The tubular exterior is rotated so that the open end of the tubular exterior faces upward; and (e) through the open end of the tubular exterior of the battery laminate. Connect the electrode terminals to the end faces in the stacking direction.

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 an image diagram showing one form of each process included in the method for manufacturing a series-stacked all-solid-state battery of the present disclosure. FIG. 2 is a schematic cross-sectional view showing one form of the battery laminate according to the present disclosure.

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-stacked all-solid-state battery of the present disclosure includes the following steps (a) to (e):
(A) Semi-cylindrical cartridge for accommodating the battery laminate, tubular exterior body for accommodating the battery laminate and the semi-cylindrical cartridge, and holding for holding the semi-cylindrical cartridge and the tubular exterior body. To provide a tool, where the battery laminate has two or more unit batteries connected in series, the unit battery being a positive electrode collector layer, a positive electrode active material layer, a solid electrolyte layer, The negative electrode active material layer and the negative electrode current collector layer are laminated in this order, and one end of the tubular exterior body is an open end;
(B) One or a plurality of semi-cylindrical cartridges constituting the unit battery or the unit battery in the semi-cylindrical cartridge held in the holder in an oblique state and held in the holder in an oblique state. Layers in sequence to form a battery laminate, thereby accommodating the battery laminate in a semi-cylindrical cartridge;
(C) The axis of the battery laminate and the axis of the tubular exterior body are aligned in a straight line, and the semi-cylindrical cartridge and the battery laminate are placed in an oblique state through the lower opening end of the tubular exterior body. Then, insert it into the tubular exterior body;
(D) While the tubular exterior body is held by the holder or after the tubular exterior body is removed from the holder, the tubular exterior body containing the semi-cylindrical cartridge and the battery laminate is rotated. Make sure that the open end of the tubular exterior is facing up; and (e) connect the electrode terminals to the end face of the battery laminate in the stacking direction through the open end of the tubular exterior.

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. Point in the direction perpendicular to.

<Step (a)>
In the step (a), a semi-cylindrical cartridge for accommodating the battery laminate, a tubular exterior body for accommodating the battery laminate and the semi-cylindrical cartridge, and the semi-cylindrical cartridge and the tubular exterior body are held. Provides a retainer for.

For example, FIG. 1 is an image diagram showing one form of each step included in the method for manufacturing a series-stacked all-solid-state battery of the present disclosure. FIG. 1A is an image diagram showing one form of step (a).

More specifically, in FIG. 1A, the semi-cylindrical cartridge 11, the battery laminate 20, and the semi-cylindrical cartridge 11 for accommodating the battery laminate 20 (shown in FIG. 1B) are provided. The embodiment which provides the cylindrical exterior body 12 for accommodating, and the holding tool 30 for holding the semi-cylindrical cartridge 11 and the tubular exterior body 12 is shown.

(Battery laminate)
In the present disclosure, the battery laminate has two or more unit batteries connected in series, and the unit battery includes a positive electrode current collector layer, a positive electrode active material layer, a solid electrolyte layer, and a negative electrode active material layer. And the negative electrode current collector layer is laminated in this order. The details will be described in the section of "series laminated all-solid-state battery" described later.

(Semi-cylindrical cartridge)
The semi-cylindrical cartridge is for accommodating the battery laminate.

In the present disclosure, the term "semi-cylindrical" means a shape in which a tubular member is divided along a vertical direction (axial direction), and does not necessarily mean a shape of a half portion of the tubular member. is not. Further, the "cylindrical shape" may be a cylindrical shape or a square tubular shape.

Both ends of the semi-cylindrical cartridge may be fully open, for example at both ends of the semi-cylindrical cartridge 11 shown in FIG. 1 (a), or at least one end may be partially open. It may have been done. In the latter case, the semi-cylindrical cartridge may be partially opened and opened to such an extent that the electrode terminals can be connected to the end face of the battery laminate in the stacking direction through the end portion.

The material constituting the semi-cylindrical cartridge is preferably an insulating material. In particular, when a metal tubular exterior body is used, it is preferable because it can prevent a short circuit between the tubular exterior body and the current collector layer. In addition, "insulation property" refers to both electron insulation property and ion insulation property.

More specifically, the material constituting the semi-cylindrical cartridge may be, for example, resin or ceramics. Examples of the resin include polypropylene, polyethylene, polyvinylidene chloride, polystyrene, polyurethane, Teflon (registered trademark), acrylic, polyphenylsulfone, polysulfone, polyarylate, polyetherimide, peak, polyphenylene sulfide (PPS), polyamideimide, and the like. Examples thereof include, but are not limited to, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride and the like. Further, examples of the ceramics include, but are not limited to, alumina, silica, zirconia and the like.

(Cylindrical exterior)
The tubular exterior body is for accommodating a battery laminate and a semi-cylindrical cartridge.

One end of the tubular exterior body is an open end. For example, in the tubular exterior body 12 shown in FIG. 1A, one end 12a is an open end.

The open end of the tubular exterior body serves as a path for inserting the semi-cylindrical cartridge and the battery laminate into the tubular exterior body in the step (c) described later. Then, in the step (e) described later, the electrode terminals can be connected to the end faces of the battery laminate in the stacking direction through the open end portion.

In the present disclosure, the state of "opening" may be a state of being completely open or a state of being partially open.

Further, the other end of the tubular exterior body other than the open end may be an open end, or may be an end sealed with a necessary component such as an electrode terminal. When the other end is an open end, the semi-cylindrical cartridge and the battery laminate in the step (c) described later are inserted into the tubular exterior body, and before being rotated, for example, an electrode terminal. It can be sealed with necessary parts such as.

The material constituting the tubular exterior body is not particularly limited, and may be, for example, metal or fiber reinforced plastic. Examples of the metal include, but are not limited to, materials having appropriate rigidity such as aluminum, aluminum alloy, and stainless steel. 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 tubular 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 tubular exterior body is used, an embodiment having an insulating layer on the inner wall thereof is preferable because it can prevent a short circuit between the tubular exterior body and the current collector layer. It is also possible to prevent a short circuit by using an insulating cartridge instead of the insulating layer or by performing an insulating treatment on the end of each layer of the battery laminate.

(Holder)
The holder is not particularly limited as long as it can hold the semi-cylindrical cartridge and the tubular exterior body, and may be in any embodiment.

Further, the holder may be rotatable while holding the semi-cylindrical cartridge and the tubular exterior body.

For example, the holder 30 shown in FIG. 1 (a) can hold the semi-cylindrical cartridge 11 and the tubular exterior body 12. In this case, the holder 30 is rotatable at the holding portion 30a of the connection between the semi-cylindrical cartridge 11 and the tubular exterior body 12.

<Step (b)>
In the step (b), the semi-cylindrical cartridge is held in the holder in an oblique state, and is placed in the semi-cylindrical cartridge held in the holder in an oblique state to form a unit battery or a unit battery. One or a plurality of layers are laminated in order to form a battery laminate, whereby the battery laminate is housed in a semi-cylindrical cartridge.

FIG. 1B is an image diagram showing one form of step (b). In FIG. 1B, the semi-cylindrical cartridge 11 is held in the holder 30 in an oblique state, and the unit battery is placed in the semi-cylindrical cartridge 11 held in the holder 30 in an oblique state. An embodiment is shown in which a plurality of constituent layers are sequentially laminated to form a battery laminate 20, whereby the battery laminate 20 is housed in a semi-cylindrical cartridge 11.

As described above, in the step (b), the unit battery or one or a plurality of layers constituting the unit battery are sequentially laminated to form the battery laminate in the semi-cylindrical cartridge, thereby forming the battery laminate. It is possible to prevent the material from falling off due to friction between the end of the layer and the semi-cylindrical cartridge.

Further, since the semi-cylindrical cartridge is held in an oblique state, when stacking one or a plurality of layers constituting the unit battery or the unit battery in order, it is easy to align the stacking positions by the weight of each layer.

In the present disclosure, the "oblique state" refers to a state in which the longitudinal direction of the object is neither parallel nor perpendicular to the horizontal direction, and the angle between the longitudinal direction of the object and the horizontal direction is more than 0 ° and less than 90 °. be.

For example, the oblique state of the semi-cylindrical cartridge means that the longitudinal direction (axial direction) of the semi-cylindrical cartridge is neither parallel nor vertical to the horizontal direction, and the longitudinal direction and the horizontal direction of the semi-cylindrical cartridge. The angle between and is greater than 0 ° and less than 90 °. More specifically, this angle may be, for example, more than 0 °, 15 ° or more, 30 ° or more, 45 ° or more, 60 ° or more, or 75 ° or more, and less than 90 °, 75 ° or less, 60 °. Hereinafter, it may be 45 ° or less, 30 ° or less, or 15 ° or less.

After the step (b) and before the step (c), one or a plurality of paired semi-cylindrical cartridges are placed on the exposed battery laminate portion from the semi-cylindrical cartridge. You may use and cover it. As a result, the battery laminate is housed by the two semi-cylindrical cartridges, so that when the battery laminate is inserted into the tubular exterior in step (c), the ends of the battery laminate are completely protected. The worry of material falling off is suppressed.

Further, the active material layer and the solid electrolyte layer among the layers 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, the 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), the axis of the battery laminate and the axis of the tubular exterior body are aligned in a straight line, and the semi-cylindrical cartridge and the battery laminate are inserted through the lower opening end of the tubular exterior body. Insert it into the tubular exterior body at an angle.

FIG. 1 (c) is an image diagram showing one form of step (c). In FIG. 1 (c), the shaft of the battery laminate 20 and the shaft of the tubular exterior body 12 are arranged in a straight line, and the semi-cylindrical cartridge 11 is passed through the lower opening end portion 12a of the tubular exterior body 12. The mode in which the battery laminate 20 is inserted into the tubular exterior body 12 in an oblique state is shown.

Here, the "axis of the battery laminate" refers to the central axis in the stacking direction of the battery laminate. Further, the "axis of the tubular exterior body" refers to the central axis in the longitudinal direction of the tubular exterior body.

Further, the insertion means is not particularly limited, and the semi-cylindrical cartridge and the battery laminate may be pushed in.

For example, as shown in FIG. 1 (c), the semi-cylindrical cartridge and the battery laminate are inserted into the tubular exterior body by the push rod 31.

As described above, in the step (c), the battery laminate end portion is inserted by inserting the semi-cylindrical cartridge and the battery laminate into the tubular exterior body while the battery laminate is housed in the semi-cylindrical cartridge. And friction with the tubular exterior body can be prevented. Therefore, it is possible to suppress the material from falling off from the end portion of the battery laminate due to friction, and it is possible to prevent the tubular exterior body from being contaminated due to friction.

<Step (d)>
In step (d), the tubular exterior body contains the semi-cylindrical cartridge and the battery laminate while the tubular exterior body is held by the holder or after the tubular exterior body is removed from the holder. Rotate the body so that the open end of the tubular exterior is facing up.

FIG. 1D is an image diagram showing one form of step (d). In FIG. 1D, in a state where the tubular exterior body 12 is held by the holder 30, the cylindrical exterior body 12 accommodating the semi-cylindrical cartridge 11 and the battery laminate 20 is rotated to form a cylinder. An aspect is shown in which the open end portion 12a of the outer body 12 is directed upward.

Further, in the step (c) described above, after the semi-cylindrical cartridge and the battery laminate are inserted into the tubular exterior body, the semi-cylindrical cartridge and the battery laminate are pressed against the electrode terminals and the like. It is preferable to rotate the tubular exterior body that houses the battery.

The direction in which the tubular exterior body is rotated is not particularly limited, and it is preferable to rotate the tubular exterior body so that the open end portion of the tubular exterior body faces upward most quickly according to the oblique state of the tubular exterior body. For example, when viewed from the front, if the open end of the tubular exterior is facing diagonally downward to the left, the tubular exterior may be rotated clockwise and the open end of the tubular exterior is diagonally downward to the right. If facing, the tubular exterior may be rotated counterclockwise.

After rotating the tubular exterior body, the one used for the insertion means in the above-mentioned step (c), for example, the push rod 31 shown in FIG. 1 (c), is removed, and the tubular exterior body is made of necessary parts. It is preferable to seal the body.

<Process (e)>
In the step (e), the electrode terminals are connected to the end face of the battery laminate in the stacking direction through the open end of the tubular exterior body.

FIG. 1 (e) is an image diagram showing one form of the step (e). FIG. 1 (e) shows an embodiment in which the electrode terminal 14 is connected to the end face of the battery laminate 20 in the stacking direction through the open end portion 12a of the tubular exterior body 12.

If necessary, other parts may be attached before connecting the electrode terminals. For example, as shown in FIG. 1 (e), an electrode plate 16, a conductive elastic body 15 such as a metal spring, or the like may be attached before connecting the electrode terminal 14.

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

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 (e). The pressing step is a step of pressing the battery laminate in the stacking direction of the battery laminate.

In this case, for example, in the battery laminate 20 shown in FIG. 1 (e), before, during, or after the step (e), along the stacking direction and toward the end face to which the electrode terminal 13 is connected. The battery laminate 20 may be pressed (not shown).

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.

FIG. 2 is a schematic cross-sectional view showing one form of the battery laminate according to the present disclosure.

The battery laminate 10 shown in FIG. 2 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 FIG. 2, the unit battery 6a and the unit battery 6b share a positive electrode / negative electrode current collector layer 5a (1b), and the unit battery 6b and the unit battery 6c share a positive electrode / negative electrode. The current collector layer 5b (1c) is shared.

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, at the time of 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 / Negative Electrode Collector Layer 2a, 2b, 2c, 2d, 2e Negative Electrode Active Material Layer 3a, 3b, 3c, 3d, 3e Solid Electrode Layer 4a, 4b, 4c, 4d 4e Positive electrode active material layer 6a, 6b, 6c Unit battery 10, 20 Battery laminate 11 Semi-cylindrical cartridge 12 Cylindrical exterior 13, 14 Electrode terminal 15 Electrode terminal 16 Electrode plate 30 Holder 31 Push rod

Claims (1)

A method for manufacturing a series-stacked all-solid-state battery, which comprises the following steps (a) to (e):
(A) Holds a semi-cylindrical cartridge for accommodating a battery laminate, a tubular exterior body for accommodating the battery laminate and the semi-cylindrical cartridge, and the semi-cylindrical cartridge and the tubular exterior body. Provided to provide a holder for the above, wherein the battery laminate has two or more unit batteries connected in series, wherein the unit battery is a positive electrode collector layer, a positive electrode active material. The layer, the solid electrolyte layer, the negative electrode active material layer, and the negative electrode current collector layer are laminated in this order, and one end of the tubular exterior body is an open end portion;
(B) The unit battery or the unit battery is placed in the semi-cylindrical cartridge which holds the semi-cylindrical cartridge in the holder in an oblique state and is held in the holder in an oblique state. To form the battery laminate by sequentially stacking one or a plurality of layers constituting the above, thereby accommodating the battery laminate in the semi-cylindrical cartridge;
(C) The semi-cylindrical cartridge and the battery laminate are arranged so that the shaft of the battery laminate and the axis of the tubular exterior body are aligned in a straight line, and the shaft of the semi-cylindrical cartridge and the battery laminate are passed through the lower opening end of the tubular exterior body. Is inserted into the tubular exterior body in an oblique state;
(D) The semi-cylindrical cartridge and the battery laminate are housed in a state where the tubular exterior body is held by the holder or after the tubular exterior body is removed from the holder. The tubular exterior is rotated so that the open end of the tubular exterior faces upward; and (e) through the open end of the tubular exterior of the battery laminate. Connect the electrode terminals to the end faces in the stacking direction.

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