JP2021136214A - Multilayer electrode body, all-solid battery with multilayer electrode body, and method for manufacturing multilayer electrode body - Google Patents

Abstract

To provide: a multilayer electrode body which enables the increase in battery capacity by reducing the thickness of a solid electrolyte layer which covers a peripheral side face of a positive electrode layer and a peripheral side face of a negative electrode layer, and which can suppress an internal short circuit; an all-solid battery with the multilayer electrode body; and a method for manufacturing the multilayer electrode body.SOLUTION: A multilayer electrode body 1 comprises: a positive electrode layer 2; a negative electrode layer 3; a solid electrolyte layer 4; and a solid electrolyte layer 5. The solid electrolyte layers 4, 5 are relatively thin and therefore, the battery capacity is increased. The solid electrolyte layer 5 covers a peripheral side face of the positive electrode layer 2 or negative electrode layer 3 and as such, an internal short circuit is suppressed. The multilayer electrode body 1 is manufactured by: filling a powdery electrode material X in a mortar hole 101a to form the negative electrode layer 3; thinly spraying a powdery solid electrolyte material W to an upper face of the negative electrode layer 3 and an inner peripheral face of the mortar hole 101a to form the solid electrolyte layers 4, 5; and filling a powdery electrode material Y in a space surrounded by the solid electrolyte layer 4 and the solid electrolyte layer 5 to form the positive electrode layer 2.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a laminated electrode body having a solid electrolyte layer, an all-solid-state battery provided with the laminated electrode body, and a method for manufacturing the laminated electrode body.

An all-solid-state battery is assembled by accommodating a laminated electrode body in which a solid electrolyte layer is arranged between a positive electrode layer and a negative electrode layer in a battery container. The laminated electrode body is formed by pressurizing a powdery electrode material for forming a positive electrode layer, a powdery electrode material for forming a negative electrode layer, and a powdery solid electrolyte material.

The solid electrolyte layer of the laminated electrode body should be relatively thin in order to improve the battery capacity. However, if the solid electrolyte layer is to be formed thinly, the laminated electrode body is likely to be cracked during pressure molding. Further, the solid electrolyte layer is more likely to cause unevenness even when pressure-molded than when it is formed to be relatively thick. Therefore, the thickness of the solid electrolyte layer is unlikely to be uniform. Cracks in the laminated electrode body and non-uniform thickness of the solid electrolyte layer reduce the battery performance of the all-solid-state battery.

Further, with the laminated electrode body housed in the battery container, there is a gap between the outer peripheral surface of the laminated electrode body and the inner peripheral surface of the battery container. Therefore, when the positive electrode active material particles are desorbed from the positive electrode layer, or when the negative electrode active material particles are desorbed from the negative electrode layer, an internal short circuit may occur when they come into contact with the opposite electrode layers.

Japanese Unexamined Patent Publication No. 2009-64644 discloses an all-solid-state lithium secondary battery provided with a lithium ion-conducting solid electrolyte layer having a shape covering at least one of the positive electrode and the negative electrode (Patent Document 1). .. Since the all-solid-state lithium secondary battery is provided with a lithium ion conductive solid electrolyte layer that covers the peripheral side surface of the electrode, it is possible to suppress the occurrence of an internal short circuit due to the detachment of the positive electrode active material particles or the negative electrode active material particles.

Japanese Unexamined Patent Publication No. 2010-282803 discloses a method for manufacturing an all-solid-state lithium ion secondary battery in which a powder material of an electrode material and a powder material of a solid electrolyte are charged and sprayed onto the surface of a current collector (Patent Document 2). ). As a result, in the manufacturing method of the all-solid-state lithium-ion secondary battery, a layer of powder can be formed with a uniform thickness, and pressure during molding is applied to the entire surface, so that cracking during pressure molding can be suppressed. can. Therefore, according to the method for manufacturing an all-solid-state lithium-ion secondary battery, the solid electrolyte layer arranged between the positive electrode layer and the negative electrode layer can be formed thinly.

Further, Japanese Patent Application Laid-Open No. 2019-21428 discloses a coin-shaped battery in which the solid electrolyte layer of the laminated body has an average thickness of 5 μm or more and 100 μm or less (Patent Document 3). The laminate of the coin-shaped battery is formed by imprinting powder, which is a material for forming the solid electrolyte layer, on the screen to charge the mixture and adhering the powder to the printed matter. As a result, the solid electrolyte layer arranged between the positive electrode layer and the negative electrode layer can be formed thinly.

Japanese Unexamined Patent Publication No. 2009-64644 Japanese Unexamined Patent Publication No. 2010-282803 Japanese Unexamined Patent Publication No. 2019-21428

However, among the solid electrolyte layers of the all-solid-state lithium secondary battery described in Patent Document 1, the solid electrolyte layer on the side surface covering the side surface of the electrode forms a space for filling the electrode on the upper surface of the columnar solid electrolyte layer. It is formed by pressurizing with a mold provided with a convex portion for forming. Therefore, if the diameter of the convex portion of the mold is made slightly smaller than the diameter of the upper surface of the solid electrolyte layer in an attempt to form the solid electrolyte layer on the side surface side thin in the radial direction, the solid electrolyte layer on the side surface side is appropriately formed. It collapses without being done. Therefore, in the all-solid-state lithium secondary battery, it was difficult to form the solid electrolyte layer on the side surface side thinly.

Further, although the all-solid lithium ion secondary battery described in Patent Document 2 and the coin-shaped battery described in Patent Document 3 can form a thin solid electrolyte layer arranged between the positive electrode layer and the negative electrode layer, It has been difficult to form a thin solid electrolyte layer that covers the peripheral side surface of the positive electrode layer and the peripheral side surface of the negative electrode layer by simply injecting or adhering the powder for forming the solid electrolyte layer from above. Further, although the coin-type battery is provided with a solid electrolyte layer that covers the peripheral side surface side of the positive electrode layer, the thickness of the solid electrolyte layer on the peripheral side surface side cannot be adjusted when pressure molding is performed after injection or adhesion. was difficult. Further, the bondability between the peripheral side surface of the positive electrode layer and the solid electrolyte layer on the peripheral side surface side or the bondability between the peripheral side surface and the solid electrolyte layer on the peripheral side surface side of the negative electrode layer is poor, and the solid electrolyte layer on the peripheral side surface side becomes poor. There was a possibility of peeling from the positive electrode layer or the negative electrode layer.

Therefore, in the present disclosure, a high-capacity and highly reliable laminate capable of reducing the thickness of the solid electrolyte layer covering the peripheral side surface of the positive electrode layer and the peripheral side surface of the negative electrode layer to increase the battery capacity and suppress an internal short circuit. An object of the present invention is to provide an all-solid-state battery provided with an electrode body and a laminated electrode body, and a method for manufacturing the laminated electrode body.

In order to solve the above problems, the present disclosure is structured as follows. That is, the all-solid-state battery according to the present disclosure includes one first electrode layer of the positive electrode layer and the negative electrode layer, the other second electrode layer of the positive electrode layer and the negative electrode layer, and the first electrode layer and the second electrode layer. A first solid electrolyte layer arranged between them and a second solid electrolyte layer extending from the peripheral end of the first solid electrolyte layer along at least one peripheral side surface of the first electrode layer and the second electrode layer may be provided. The first solid electrolyte layer may have a thickness of 5 to 180 μm. The second solid electrolyte layer may have a thickness of 1 to 180 μm in the radial direction.

Preferably, the ratio of the thickness of the first solid electrolyte layer to the thickness of the positive electrode layer may be 0.03 or more.

Preferably, the ratio of the thickness of the first solid electrolyte layer to the thickness of the positive electrode layer may be 0.3 or less.

Preferably, the second solid electrolyte layer may extend along the peripheral side surface of the positive electrode layer. The peripheral side surface of the negative electrode layer may be exposed.

The all-solid-state battery according to the present disclosure may include a battery container and a laminated electrode body housed in the internal space of the battery container.

The method for manufacturing a laminated electrode body according to the present disclosure includes a die having a mortar hole penetrating vertically, a lower pestle that is inserted from below the mortar hole and slides in the mortar hole, and is inserted from above the mortar hole. It may include a step of preparing a pressurizing device including an upper pestle that slides in the mortar. The step of forming one of the positive electrode layer and the negative electrode layer by filling the mortar hole with the first electrode material in a state where the lower opening of the mortar hole is closed by the lower punch may be included. By adhering a solid electrolyte material to the upper surface of the first electrode layer and the inner peripheral surface of the ulcer from above the acetabulum, the first solid electrolyte layer is formed on the upper surface of the first electrode layer, and the inside of the acetabulum is formed. A step of forming a second solid electrolyte layer on the peripheral surface may be included. The step of forming the other second electrode layer of the positive electrode layer and the negative electrode layer by filling the space surrounded by the first solid electrolyte layer and the second solid electrolyte layer with the second electrode material may be included. The step of forming a laminated electrode body by pressurizing the first electrode layer, the second electrode layer, the first solid electrolyte layer, and the second solid electrolyte layer with the lower and upper punches may be included. The step of taking out the laminated electrode body from the mortar by moving at least one of the upper and lower pestle and the die relative to each other may be included.

Preferably, the step of forming the first electrode layer by filling the mortar with the first electrode material and then pressurizing the first electrode layer with the upper and lower pestle before attaching the solid electrolyte material. May include.

Preferably, in the step of forming the first solid electrolyte layer and the second solid electrolyte layer, the solid electrolyte material may be attached in advance to the lower surface of the upper punch facing the upper surface of the first electrode layer. The first solid electrolyte layer may be formed on the upper surface of the first electrode layer by moving the upper punch toward the upper surface of the first electrode layer and applying pressure. A second solid electrolyte layer may be formed by adhering a solid electrolyte material to the inner peripheral surface of the acetabulum.

Preferably, further, before filling the mortar with the first electrode material, the inner peripheral surface of the mortar is adhered by adhering the solid electrolyte material in a state where the opening below the mortar is closed by the first lower punch. May include a step of forming a second solid electrolyte layer on the side of the first electrode layer and forming a third solid electrolyte layer on the upper surface of the first lower punch. The step of removing the first lower pestle together with the third solid electrolyte layer from below the mortar and inserting the second lower pestle from below the mortar so as to contact the lower end of the second solid electrolyte layer on the first electrode layer side is included. It's fine. In the step of filling the mortar with the first electrode material, the first electrode material is filled in the space surrounded by the second solid electrolyte layer on the inner peripheral surface of the mortar and the upper surface of the second lower pestle. One electrode layer may be formed. Before forming the first solid electrolyte layer and the second solid electrolyte layer on the second electrode layer side, a space for adhering the solid electrolyte material is provided on the inner peripheral surface of the molar hole and the upper surface of the first electrode layer. May include the step of forming in.

According to the laminated electrode body and the all-solid-state battery provided with the laminated electrode body according to the present disclosure, the thickness of the solid electrolyte layer covering at least one of the peripheral side surface of the positive electrode layer and the peripheral side surface of the negative electrode layer is reduced in the radial direction of the battery. The capacity can be increased and an internal short circuit can be suppressed. According to the method for manufacturing a laminated electrode body, the radial thickness of the solid electrolyte layer covering at least one of the peripheral side surface of the positive electrode layer and the peripheral side surface of the negative electrode layer is thinned to increase the battery capacity and suppress an internal short circuit. It is possible to provide a laminated electrode body capable of providing a laminated electrode body.

FIG. 1 is a cross-sectional view showing the structure of the all-solid-state battery according to the present disclosure. FIG. 2 is a cross-sectional view showing the structure of the laminated electrode body shown in FIG. FIG. 3 is a schematic view showing a method for manufacturing the laminated electrode body shown in FIG. FIG. 4 is a schematic view showing a method for manufacturing the laminated electrode body shown in FIG. FIG. 5 is a schematic view showing a method for manufacturing the laminated electrode body shown in FIG. FIG. 6 is a schematic view showing a method for manufacturing the laminated electrode body shown in FIG. FIG. 7 is a schematic view showing a method for manufacturing the laminated electrode body shown in FIG. FIG. 8 is a cross-sectional view showing the structure of another laminated electrode body. FIG. 9 is a schematic view showing another manufacturing method of the laminated electrode body shown in FIG. FIG. 10 is a schematic view showing another manufacturing method of the laminated electrode body shown in FIG. FIG. 11 is a schematic view showing another manufacturing method of the laminated electrode body shown in FIG. FIG. 12 is a schematic view showing another manufacturing method of the laminated electrode body shown in FIG. FIG. 13 is a schematic view showing another manufacturing method of the laminated electrode body shown in FIG.

Hereinafter, a method for manufacturing the all-solid-state battery 10 and the laminated electrode body 1 including the laminated electrode body 1 and the laminated electrode body 1 according to the present disclosure will be specifically described with reference to FIGS. 1 to 13. First, the all-solid-state battery 10 and the laminated electrode body 1 included in the all-solid-state battery 10 according to the present disclosure will be specifically described with reference to FIGS. 1 and 2. As shown in FIG. 1, the all-solid-state battery 10 includes an outer can 20, a sealing can 30, a laminated electrode body 1, and a gasket 40. The all-solid-state battery 10 is a flat battery.

The outer can 20 includes a circular bottom portion 21 and a cylindrical peripheral wall portion 22 formed continuously from the outer periphery of the bottom portion 21. The peripheral wall portion 22 is provided so as to extend substantially perpendicular to the bottom portion 21 in a vertical cross-sectional view. The outer can 20 is made of a metal material such as stainless steel, nickel, or iron. The shape of the outer can 20 is not limited to the cylindrical shape provided with the circular bottom portion 21. For example, the shape of the outer can 20 may be such that the bottom portion 21 is formed in a polygonal shape such as a quadrangular shape, and the peripheral wall portion 22 is formed in a polygonal tubular shape such as a square cylinder that matches the shape of the bottom portion 21. Various changes can be made according to the size and shape of the battery 10. Therefore, the shape of the peripheral wall portion 22 includes not only a cylindrical shape but also a polygonal tubular shape such as a square tubular shape.

The sealing can 30 includes a circular flat surface portion 31 and a cylindrical peripheral wall portion 32 formed continuously from the outer periphery of the flat surface portion 31. The opening of the sealing can 30 faces the opening of the outer can 20. The sealing can 30 is made of a metal material such as stainless steel. The shape of the sealing can 30 is not limited to the cylindrical shape provided with the circular flat surface portion 31. For example, the shape of the sealing can 30 may be such that the flat surface portion 31 is formed in a polygonal shape such as a quadrangular shape, and the peripheral wall portion 32 is formed in a polygonal tubular shape such as a square tubular shape that matches the shape of the flat surface portion 31. Various changes can be made according to the size and shape of the all-solid-state battery 10. Therefore, the shape of the peripheral wall portion 32 includes not only a cylindrical shape but also a polygonal tubular shape such as a square tubular shape.

The peripheral wall portion 32 of the sealing can 30 has a base end portion 32a on the flat surface portion 31 side, a diameter-expanded portion 32b on the opening end side formed larger than the outer diameter of the base end portion 32a, and a base end portion 32a. It has a stepped portion 32c between the portion 32b and the portion 32b. Therefore, the peripheral wall portion 32 is formed in a stepped shape in which the enlarged diameter portion 32b is wider outward than the base end portion 32a.

The outer can 20 and the sealing can 30 are accommodated in the internal space of the laminated electrode body 1 and then caulked between the peripheral wall portion 22 of the outer can 20 and the peripheral wall portion 32 of the sealing can 30 via a gasket 40. Specifically, the outer can 20 and the sealing can 30 have the openings of the outer can 20 and the sealing can 30 facing each other, and the peripheral wall portion 32 of the sealing can 30 is inserted inside the peripheral wall portion 22 of the outer can 20. Later, it is crimped between the peripheral wall portion 22 and the peripheral wall portion 32 via the gasket 40. The edge portion of the peripheral wall portion 22 is crimped so as to face inward in the direction of the step portion 32c of the peripheral wall portion 32. Therefore, the edge portion of the peripheral wall portion 22 can be sufficiently crimped in a direction substantially perpendicular to the radial direction of the tubular side wall portion 22, that is, in the vertical direction. In this way, the battery container is formed by the outer can 20 and the sealing can 30.

The gasket 40 is formed of a low moisture permeable resin such as polypropylene resin, polyphenylene sulfide resin, and PFA resin. The gasket 40 is formed in a tubular shape along the inner peripheral surface of the peripheral wall portion 22 of the outer can 20, and is arranged between the peripheral wall portion 22 of the outer can 20 and the peripheral wall portion 32 of the sealing can 30. The gasket 40 is not particularly limited as long as it can insulate the outer can 20 and the sealing can 30, but a polyphenylene sulfide resin or a fluororesin such as a PFA resin is preferably used from the viewpoint of moisture permeability and heat resistance. ..

As shown in FIGS. 1 and 2, the laminated electrode body 1 is a solid arranged between a positive electrode layer (electrode layer) 2, a negative electrode layer (electrode layer) 3, and a positive electrode layer 2 and a negative electrode layer 3. It includes an electrolyte layer 4 and a solid electrolyte layer 5 extending from the peripheral end of the solid electrolyte layer 4 along the peripheral side surface of the positive electrode layer 2. The positive electrode layer 2, the negative electrode layer 3, and the solid electrolyte layer 4 have substantially similar circular shapes in a plan view, and the positive electrode layer 2, the solid electrolyte layer 4, and the negative electrode layer 3 are formed from the bottom surface 21 side of the positive electrode can 20 from the lower side shown in the drawing. They are stacked in order. That is, the laminated electrode body 1 has a cylindrical shape. The positive electrode layer 2 of the laminated electrode body 1 is arranged on the upper surface of the bottom portion 21 of the outer can 20. Therefore, the outer can 20 functions as a positive electrode can. Further, the negative electrode layer 3 of the laminated electrode body 1 faces the lower surface of the flat surface portion 31 of the sealing can 30. Therefore, the sealing can 30 functions as a negative electrode can. The laminated electrode body 1 is not limited to the cylindrical shape, and can be variously changed according to the size and shape of the all-solid-state battery 10, such as a rectangular parallelepiped shape and a polygonal prism shape. Further, the laminated electrode body 1 may be arranged so that the negative electrode layer 3 is positioned on the outer can 20 side and the positive electrode layer 2 is positioned on the sealing can 30 side. In that case, the outer can 20 functions as a negative electrode can, and the sealing can 30 functions as a positive electrode can.

The positive electrode layer 2 contains, for example, lithium cobalt oxide having an average particle size of 5 μm, a sulfide-based solid electrolyte (Li ₆ PS ₅ Cl), and carbon as a conductive auxiliary agent as positive electrode active materials used in a lithium ion secondary battery. It is a positive electrode pellet formed into a columnar shape by putting a 92 mg positive electrode mixture containing an nanotube in a mass ratio of 70:26: 4 into a mold having a diameter of 8 mm. The positive electrode layer 2 is not particularly limited as long as it can function as the positive electrode layer 2 of the laminated electrode body 1, and is, for example, lithium cobalt oxide, lithium nickel oxide, lithium manganate, or spinel-type manganese composite oxide. , Olivin type composite oxide and the like, and these may be appropriately mixed. Further, the size and shape of the positive electrode layer 2 are not limited to the cylindrical shape, and can be variously changed according to the size and shape of the all-solid-state battery 1.

The negative electrode layer 3 contains, for example, LTO (Li ₄ Ti ₅ O ₁₂ , lithium titanate), a sulfide-based solid electrolyte (Li ₆ PS ₅ Cl), and carbon as negative electrode active materials used in a lithium ion secondary battery. It is a negative electrode pellet obtained by molding 129 mg of a negative electrode mixture containing an nanotube in a weight ratio of 50:41: 9 into a cylindrical shape. The negative electrode layer 3 is not particularly limited as long as it can function as the negative electrode layer 3 of the laminated electrode body 1, and is not particularly limited, for example, a metal material such as metallic lithium or lithium alloy, graphite, low crystal carbon, or the like. It may be a carbon material, SiO, LTO (Li ₄ Ti ₅ O ₁₂ , lithium titanate) or the like, or a mixture thereof as appropriate. Further, the size and shape of the negative electrode layer 3 are not limited to the cylindrical shape, and can be variously changed according to the size and shape of the all-solid-state battery 1.

The solid electrolyte layer 4 and the solid electrolyte layer 5 are, for example, _{formed by molding 1 mg of a sulfide-based solid electrolyte (Li 6} PS ₅ Cl) into a cylindrical shape. The solid electrolyte layer 4 and the solid electrolyte layer 5 are not particularly limited, but may be other sulfide-based solid electrolytes such as algyrodite type from the viewpoint of ionic conductivity. When a sulfide-based solid electrolyte is used, it is preferable to coat the surface of the positive electrode active material with niobium oxide in order to prevent the reaction with the positive electrode active material. Further, the solid electrolyte layer 4 and the solid electrolyte layer 5 may be a hydride-based solid electrolyte, an oxide-based solid electrolyte, or the like. Further, the size and shape of the solid electrolyte layer 4 are not limited to the cylindrical shape, and can be variously changed according to the size and shape of the all-solid-state battery 1.

The solid electrolyte layer 4 is arranged between the positive electrode layer 2 and the negative electrode layer 3. As shown in FIG. 2, the thickness t1 of the solid electrolyte layer 4 is 5 μm to 180 μm. The thickness t1 of the solid electrolyte layer 4 is 5 μm or more, preferably 10 μm or more, more preferably 20 μm in order to form the solid electrolyte layer 4 with a uniform thickness and prevent a short circuit occurring between the positive electrode layer and the negative electrode layer. It is better to do the above. On the other hand, if the solid electrolyte layer 4 becomes too thick, the ratio of the positive electrode layer 2 and the negative electrode layer 3 to the entire laminated electrode body 1 decreases, and the battery capacity per volume of the laminated electrode body 1 decreases. In addition, the discharge characteristics deteriorate due to the increase in resistance due to the solid electrolyte layer 4. Therefore, the thickness t1 of the solid electrolyte layer 4 is preferably 180 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

The solid electrolyte layer 5 may extend from the peripheral end of the solid electrolyte layer 4 along at least one peripheral side surface of the positive electrode layer 2 and the negative electrode layer 3. As shown in FIG. 2, when the solid electrolyte layer 5 is provided on the peripheral side surface of the positive electrode layer 2, the radial size of the negative electrode layer 3 can be made larger than that of the positive electrode layer 2 in a plan view. That is, from the peripheral end of the solid electrolyte layer 4 to the peripheral side surface of the positive electrode layer 2 so that the radial size of the positive electrode layer 2 and the solid electrolyte layer 5 combined is the same as the radial size of the negative electrode layer 3. The solid electrolyte layer 5 can also be extended along the line. As shown in FIG. 2, the solid electrolyte layer 4 and the solid electrolyte layer 5 have a substantially U-shape in a vertical cross-sectional view. The solid electrolyte layer 5 has a cylindrical shape that covers the peripheral side surface of the positive electrode layer 2. As a result, it is possible to suppress a short circuit that may occur when the positive electrode active material particles are desorbed from the peripheral side surface of the positive electrode layer 2 and come into contact with the peripheral side surface of the negative electrode layer 3. The radial thickness t2 of the solid electrolyte layer 5 is set to 1 μm or more, preferably 5 μm or more, and more preferably 10 μm or more in order to prevent the active material particles from being detached from the positive electrode layer 2 or the negative electrode layer 3. Is good. On the other hand, if the solid electrolyte layer 5 becomes too thick, the ratio of the positive electrode layer 2 and the negative electrode layer 3 to the entire laminated electrode body 1 decreases, and the battery capacity per volume of the laminated electrode body 1 decreases. Therefore, the radial thickness t2 of the solid electrolyte layer 5 is preferably 180 μm or less, preferably 50 μm or less, and more preferably 30 μm or less. The solid electrolyte layer 5 does not necessarily have to be composed of only the solid electrolyte. For example, the solid electrolyte layer 5 exhibits its function even if some active materials of the electrode layer on which the solid electrolyte layer 5 is formed are mixed. Is possible.

The ratio R (t1 / t3) of the thickness t1 of the solid electrolyte layer 4 to the thickness t3 of the positive electrode layer 2 is preferably 0.03 or more. At the time of molding, the positive electrode layer 2 is pressurized so as to have a filling density of a certain level or higher. The pressure on the positive electrode layer 2 increases as the thickness t3 of the positive electrode layer 2 increases. Therefore, if the thickness t3 of the positive electrode layer 2 is too thick, that is, if the ratio R is too small, when the positive electrode layer 2 and the solid electrolyte layer 4 are pressed together, an excessive pressure is applied to the solid electrolyte layer 4. Is added. Then, the positive electrode active material particles of the positive electrode layer 2 bite into the solid electrolyte layer 4, and there is a high risk that a short circuit occurs between the positive electrode layer 2 and the negative electrode layer 3. Therefore, the ratio R is preferably 0.03 or more, preferably 0.1 or more. On the other hand, if the thickness t1 of the solid electrolyte layer 4 is too thick, that is, if the ratio R becomes too large, the ratio of the positive electrode layer 2 and the negative electrode layer 3 to the entire laminated electrode body 1 decreases, and the laminated electrode body 1 Battery capacity per volume decreases. In addition, the discharge characteristics deteriorate due to the increase in resistance due to the solid electrolyte layer 4. Therefore, the ratio R is preferably 0.3 or less, and preferably 0.2 or less.

As shown in FIG. 1, the peripheral wall portion 32 of the sealing can 30 is located inside the peripheral wall portion 22 of the outer can 20. The solid electrolyte layer 5 is formed along the peripheral side surface of the positive electrode layer 2. That is, the solid electrolyte layer 5 covers the peripheral side surface of the positive electrode layer 2. As a result, the positive electrode active material particles are separated from the positive electrode layer 2, and a short circuit that may occur in contact with the sealing can 30 can be suppressed. On the other hand, when the laminated electrode body 1 is arranged so that the negative electrode layer 3 is positioned on the outer can 20 side and the positive electrode layer 2 is positioned on the sealing can 30 side, the solid electrolyte layer 5 is provided along the peripheral side surface of the negative electrode layer 3. It may be formed. In this way, by covering the peripheral side surface of either the positive electrode layer 2 or the negative electrode layer 3 arranged on the outer can 20 side with the solid electrolyte layer 5, internal short circuits due to contact between the sealing can 2 and the active material particles are suppressed. can do.

Next, a method for manufacturing the laminated electrode body 1 will be specifically described with reference to FIGS. 3 to 7.

First, as shown in FIG. 3, the pressurizing device 100 is prepared. The pressurizing device 100 is inserted from above the die 101 having a mortar hole 101a penetrating vertically, the lower pestle 102 inserted from below the mortar hole 101a and sliding in the mortar hole 101a, and the mortar hole 101a. It is provided with an upper pestle 103 that slides in the mortar hole 101a. The die 101 is formed in a plate shape. The mortar hole 101a is formed with a cylindrical opening from the upper surface to the lower surface of the die 101. The lower pestle 102 and the upper pestle 103 are each formed in a cylindrical shape that follows the opening shape of the usuki. The pressurizing device 100 pressurizes the material filled in the mortar hole 101a by sliding the lower pestle 102 and the upper pestle 103 in the vertical direction.

Next, as shown in FIG. 4, the lower punch 102 is inserted into the mortar hole 101a, and the electrode material X is filled from above the mortar hole 101a with the lower opening of the mortar hole 101a closed by the lower pestle 102. .. As a result, the negative electrode layer 3 before molding is formed. In this production method, the electrode material X is a powdery negative electrode compounding agent for forming the negative electrode layer 3. Although not particularly shown, the powdery electrode material X is filled in the mortar hole 101a from a hopper that moves in parallel on the upper surface of the die 101. The hopper moves above the mortar hole 101a when the electrode material X is filled, and stands by at a place other than above the mortar hole 101a when the electrode material X is not filled. The electrode material X filled in the mortar hole 101a is pressurized by the upper pestle 103 from above. The electrode material X may be in the form of powder, or may be pellets that have been pressure-treated in advance and formed to have an outer diameter substantially the same as the inner diameter of the mortar hole 101a. When the electrode material X is a pellet, the electrode material X may or may not be pressurized by the upper pestle 103 from above. Further, even if the electrode material X is in the form of powder, the pressure is not applied here, and as will be described later, the solid electrolyte material W and the electrode material Y are further put into the mill hole 101a, and then the electrode material X and the solid electrolyte material are used. W and the electrode material Y may be pressurized together.

Further, in FIG. 4, the negative electrode layer 3 is formed by using the space above the mortar hole 101a, but in reality, the negative electrode layer 3 is formed by using the space below the mortar hole 101a. Is preferable. At that time, the upper surface of the lower pestle 102 is positioned on the lower opening side of the mortar hole 101a, for example, along the lower surface of the die 101. After forming the negative electrode layer 3 in the space below the mill hole 101a, the solid electrolyte layer 4 and the solid are used in the space above the negative electrode layer 3 (the portion where the negative electrode layer 3 is formed in FIG. 4). The electrolyte layer 5 and the positive electrode layer 2 are formed. As a result, the step of arranging the negative electrode layer 3 on the upper side of the mortar hole 101a, which will be described later, on the lower side can be omitted, and the manufacturing process of the laminated electrode body 1 can be simplified.

As shown in FIG. 4, when the negative electrode layer 3 is formed by utilizing the space above the mortar hole 101a, the negative electrode layer 3 (molded body or pre-molded filler) is then subjected to. Move it to the lower side of the mortar hole 101a with the upper pestle 103 or sandwiched between the upper pestle 103 and the lower pestle 102, and as shown in FIG. 5 below, the solid electrolyte layer 4 and the solid electrolyte are on the upper side of the mortar hole 101a. A space for forming the layer 5 and the positive electrode layer 2 is formed. Alternatively, the space may be formed by removing the lower punch 102 from below the mortar hole 101a, inverting the die 101, and arranging the negative electrode layer 3 below the mortar hole 101a. That is, after the negative electrode layer 3 is formed, it is sufficient that a space in which the solid electrolyte material W can be injected can be further formed in the mortar hole 101a on the inner peripheral surface of the mortar hole 101a and the upper surface of the negative electrode layer 3.

Next, as shown in FIG. 5, the powdery solid electrolyte material W is injected from above the mortar hole 101a onto the negative electrode layer 3 and the inner peripheral surface of the mortar hole 101a by the injection device 104. The injection device 104 moves in parallel on the upper surface of the die 101 in the same manner as the above-mentioned hopper. The injection device 104 moves above the mortar hole 101a when injecting the solid electrolyte material W, and stands by at a place other than above the mortar hole 101a when the solid electrolyte material W is not injected. The injection device 104 includes an electrostatic generating electrode (not shown) having a needle-shaped or tapered tip. By applying a high DC voltage of, for example, about −20 kV to the electrode, the solid electrolyte material W can be negatively charged by the electric field formed at the tip of the electrode. The die 101 and the lower pestle 102 are charged with the opposite polarity to the charged solid electrolyte material W, whereby an adhesive layer of the solid electrolyte material W is formed. By adjusting the amount of the solid electrolyte material W adhered to the solid electrolyte layer 4 and the solid electrolyte layer 5, the thicknesses of the solid electrolyte layer 4 and the solid electrolyte layer 5 can be adjusted, and after molding, the upper surface of the electrode material X can be adjusted. The solid electrolyte layer 4 can be formed thin and the thickness can be made uniform, and the solid electrolyte layer 5 can be formed thin and the thickness can be made uniform on the inner peripheral surface of the mill hole 101a.

When it is difficult to adjust the thickness of the solid electrolyte layer 4, that is, the amount of the solid electrolyte material W adhered to the solid electrolyte layer 4 by the above method, the solid electrolyte layer 4 is formed and then the solid electrolyte layer 5 is formed. You may. That is, although not shown, the negatively charged solid electrolyte material W is attached to the lower surface of the upper punch 103 charged to the opposite polarity, and the electrode material X is further pressed by the upper punch 103 from above. As a result, the solid electrolyte material W is fixed to the upper surface of the negative electrode layer 3 to form the solid electrolyte layer 4. Next, the charged solid electrolyte material W is injected into the mortar hole 101a to adhere the solid electrolyte material W to the inner peripheral surface of the mortar hole 101a to form the solid electrolyte layer 5.

Next, as shown in FIG. 6, the space surrounded by the solid electrolyte layer 4 and the solid electrolyte layer 5 is filled with the electrode material Y. As a result, the positive electrode layer 2 before molding is formed. In this production method, the electrode material Y is a powdery positive electrode compounding agent for forming the positive electrode layer 2. Although not particularly shown, the powdery electrode material Y is filled into the mortar hole 101a from a hopper that moves in parallel on the upper surface of the die 101. The hopper moves above the mortar hole 101a when the electrode material Y is filled, and stands by at a place other than above the mortar hole 101a when the electrode material Y is not filled. The pressurizing device 100 includes a hopper filled with the electrode material X and a hopper filled with the electrode material Y, respectively. The filled electrode material Y is pressurized by the upper pestle 103 from above. As a result, a molded body of the laminated electrode body 1 is formed.

When the filled electrode material Y is pressurized from above, the above-mentioned negative electrode layer 3, the solid electrolyte layer 4 and the solid electrolyte layer 5 are also pressed together. At this time, the inner peripheral surface of the mortar hole 101a suppresses the movement of the solid electrolyte layer 5 in the radial direction, and the lower punch 102 also suppresses the downward movement of the laminated electrode body 1. Therefore, when the pressure from above by the upper punch 103 is applied to the laminated electrode body 1, the outer peripheral surface of the positive electrode layer 2 presses the solid electrolyte layer 5 against the inner peripheral surface of the mortar hole 101a in the radial direction. As a result, the solid electrolyte layer 5 can be sufficiently formed by pressurization. Further, the bondability between the positive electrode layer 2 and the solid electrolyte layer 5 can be improved, and thus the solid electrolyte layer 5 can be prevented from peeling from the positive electrode layer 2, so that the solid electrolyte layer after molding can be suppressed. The thickness of 5 can be reduced.

Finally, as shown in FIG. 7, the laminated electrode body 1 can be taken out from the mortar hole 101a by relatively moving the die 101 and the lower punch 102. Then, as shown in FIG. 1, the laminated electrode body 1 is housed between the outer can 20 and the sealing can 30, and the all-solid-state battery 10 is assembled. In order to take out the laminated electrode body 1 from the mortar hole 101a, the die 101 and the upper punch 103 may be relatively moved. Further, if the upper punch 103 and the lower punch 102 are moved relative to the die 101 with the laminated electrode body 1 sandwiched therein, and the laminated electrode body 1 is taken out from the mortar hole 101a, the laminated electrode body 1 can be taken out. It is preferable because it can prevent cracks and chips from being generated. Depending on the material of the solid electrolyte layer 5, it can be expected that the solid electrolyte acts as a lubricant, making it easier to take out the laminated electrode body 1 from the die 101.

As described above, according to the method for producing the laminated electrode body 1, the solid electrolyte layer 4 and the solid electrolyte layer 5 can be formed thinly and uniformly, and the thickness of the solid electrolyte layer 5 can be adjusted. Further, the bondability between the peripheral side surface of the positive electrode layer 2 and the solid electrolyte layer 5 can be improved. As a result, the battery capacity of the all-solid-state battery 1 can be increased. Further, it is possible to more reliably suppress the positive electrode active material particles from desorbing from the positive electrode layer 2, and to suppress an internal short circuit due to contact between the positive electrode active material particles and the negative electrode layer 3 or the negative electrode can 30. That is, according to the laminated electrode body 1 obtained by this manufacturing method, it is possible to provide an all-solid-state battery 1 having a high capacity and high reliability.

In this production method, the electrode material X forms the negative electrode layer 3 and the electrode material Y forms the positive electrode layer 2, but the electrode material X forms the positive electrode layer 2 and the electrode material Y forms the negative electrode layer 3. You can also do it.

Next, the other laminated electrode body 1 will be specifically described with reference to FIG. The other laminated electrode body 1 has the same basic configuration as the above-mentioned laminated electrode body 1. Therefore, a configuration different from the above-mentioned laminated electrode body 1 will be described.

As shown in FIG. 8, the other laminated electrode body 1 has a solid electrolyte layer 5 extending from the peripheral end of the solid electrolyte layer 4 along the peripheral side surface of the positive electrode layer 2 and the peripheral side surface of the negative electrode layer 3. The radial thickness of the solid electrolyte layer 5 is the same as that of the above-mentioned solid electrolyte layer 5 shown in FIG. The solid electrolyte layer 4 and the solid electrolyte layer 5 have a substantially H-shaped shape in a vertical cross-sectional view. As a result, it is possible to suppress the desorption of the active material particles from both the positive electrode layer 2 and the negative electrode layer 3, and it is possible to more reliably suppress the internal short circuit. As a result, according to the other laminated electrode body 1, the battery capacity can be increased, and a more reliable all-solid-state battery 1 can be provided. In particular, in a bipolar battery in which a plurality of laminated electrode bodies 1 are laminated in series, the negative electrode layer 3 of one laminated electrode body 1 of the adjacent laminated electrode bodies 1 and the positive electrode layer 2 of the other laminated electrode body 1 are adjacent to each other. Therefore, it is possible to suppress an internal short circuit between adjacent laminated electrode bodies 1.

Another manufacturing method of the laminated electrode body 1 will be described with reference to FIGS. 9 to 13.

First, the pressurizing device 100 is prepared in the same manner as in the above-mentioned manufacturing method. In this manufacturing method, the replacement lower pestle 105 shown in FIG. 9 is inserted from below the mortar hole 101a instead of the lower pestle 102.

Next, as shown in FIG. 9, the powdery solid electrolyte material W is injected from above the mortar hole 101a onto the upper surface of the replacement lower pestle 105 and the inner peripheral surface of the mortar hole 101a by the injection device 104. .. The solid electrolyte material W is negatively charged. The die 101 and the replacement lower pestle 105 are charged with the opposite polarity to the charged solid electrolyte material W. As a result, an adhesion layer of the solid electrolyte material W is formed, and the solid electrolyte layer 5 can be thinly formed on the inner peripheral surface of the mortar hole 101a. On the other hand, since the solid electrolyte layer 6 formed on the upper surface of the replacement lower pestle 105 is not used for manufacturing the laminated electrode body 1, as shown in FIG. 10, the replacement lower pestle 105 is used together with the solid electrolyte layer 6. Is removed from below the mortar 101a. After that, a lower pestle 102 different from the lower pestle 105 is inserted from below the mortar hole 101a. The upper end of the lower pestle 102 can be inserted into the mortar 101a so as to be in contact with the lower end of the solid electrolyte layer 5.

Next, as shown in FIG. 11, the space surrounded by the solid electrolyte layer 5 and the upper surface of the lower pestle 102 is filled with the electrode material X. As a result, the negative electrode layer 3 before molding is formed. In this production method, the electrode material X is a powdery negative electrode compounding agent for forming the negative electrode layer 3. Although not particularly shown, the powdery electrode material X is filled in the mortar hole 101a by the same hopper as described above. The electrode material X and the solid electrolyte layer 5 filled in the mortar hole 101a are pressed by the upper punch 103 from above, and the negative electrode layer 3 and the molded body of the solid electrolyte layer 5 arranged on the peripheral side surface of the negative electrode layer 3 are formed. It is formed. The negative electrode layer 3 and the solid electrolyte layer 5 may not be pressurized here, and the solid electrolyte material W and the electrode material Y may be put into the mortar hole 101a and then pressed together.

Next, the negative electrode layer 3 and the solid electrolyte layer 5 (molded body or filler before molding) are sandwiched between the upper punch 103 or the upper punch 103 and the lower punch 102, and the mortar hole 101a is formed. It is moved downward to form a space on the upper side of the mortar hole 101a for producing the solid electrolyte layer 4 and the solid electrolyte layer 5 shown in FIG. 12 and the positive electrode layer 2 shown in FIG. Alternatively, the space may be formed by removing the lower punch 102 from below the mortar hole 101a, inverting the die 101, and arranging the negative electrode layer 3 below the mortar hole 101a. That is, after the negative electrode layer 3 and the solid electrolyte layer 5 on the negative electrode layer 3 side are formed, a space in which the solid electrolyte material W can be injected is further formed in the mortar hole 101a on the inner peripheral surface of the mortar hole 101a and the upper surface of the negative electrode layer 3. I hope I can.

Next, as shown in FIG. 12, in the above-mentioned space, the powdery solid electrolyte material W is injected by the injection device 104 from above the molar hole 101a onto the negative electrode layer 3 and the inner peripheral surface of the molar hole 101a. Alternatively, or by fixing the solid electrolyte material W to the upper surface of the negative electrode layer 3 with the upper punch 103 and then injecting the powdery solid electrolyte material W with the injection device 104, the solid electrolyte layer 4 and the positive electrode layer 2 side. The solid electrolyte layer 5 of the above is formed. This step is the same as that described above, and detailed description thereof will be omitted.

Next, as shown in FIG. 13, the space surrounded by the solid electrolyte layer 4 and the solid electrolyte layer 5 is filled with the electrode material Y. As a result, the positive electrode layer 2 before molding is formed. The filled electrode material Y is pressurized by the upper pestle 103 from above. At this time, the negative electrode layer 3, the solid electrolyte layer 4, and the solid electrolyte layer 5 described above are also pressurized together. As a result, a molded body of the laminated electrode body 1 is formed. This step is also the same as that described above, and detailed description thereof will be omitted. The solid electrolyte layer 5 formed on the peripheral side surface of the negative electrode layer 3 and the solid electrolyte layer 5 formed on the peripheral side surface of the positive electrode layer 2 may have different thicknesses.

Finally, by relatively moving the die 101 and the lower punch 102, the laminated electrode body 1 can be taken out from the mortar hole 101a. In order to take out the laminated electrode body 1 from the mortar hole 101a, the die 101 and the upper punch 103 may be relatively moved. Further, if the upper punch 103 and the lower punch 102 are moved relative to the die 101 with the laminated electrode body 1 sandwiched therein, and the laminated electrode body 1 is taken out from the mortar hole 101a, the laminated electrode body 1 can be taken out. It is preferable because it can prevent cracks and chips from being generated. According to the laminated electrode body 1 obtained by this manufacturing method, a short circuit can be prevented more reliably, and a more reliable all-solid-state battery 1 can be provided. Also in this manufacturing method, the electrode material X may form the positive electrode layer 2 and the electrode material Y may form the negative electrode layer 3.

Although the embodiments have been described above, the present disclosure is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the embodiments.

Next, a test was conducted on the thickness of the solid electrolyte layer 4 or 5 of the laminated electrode body 1 and the presence or absence of an internal short circuit in the all-solid-state battery 10 (flat battery) containing the laminated electrode body 1.

(Example 1)
A laminated electrode body was produced by the following method using a commercially available powder compression molding machine for tablet molding. The electrode body was manufactured in an atmosphere in which the humidity was sufficiently reduced.

<Formation of negative electrode layer and solid electrolyte layer>
Lithium titanate powder having an average particle size of 2 μm was mixed at a ratio of 50 parts by mass, carbon nanotubes: 9 parts by mass, and sulfide-based solid electrolyte (Li ₆ PS ₅ Cl): 41 parts by mass to prepare a negative electrode mixture. .. The negative electrode mixture is set in a powder supply mechanism (hopper) provided in a powder compression molding machine, and a lower opening is closed with a lower punch inside the mortar of a die having a mortar having a diameter of 8 mm. In this state, the negative electrode mixture was filled with 129 mg.

_{Next, a sulfide-based solid electrolyte material (Li 6} PS ₅ Cl) is set in an injection device equipped with an electrostatic generating electrode having a needle-shaped tip of the upper pestle only, and a high DC voltage of about -20 kV is set on the electrode. Was sprayed onto the lower surface of the upper pestle only, which was charged with the opposite polarity, to attach the solid electrolyte material. The amount of the solid electrolyte material adhered at this time was about 2 mg.

Further, the negative electrode mixture in the mortar was pressed by the upper pestle with the solid electrolyte material attached to the lower surface to form the negative electrode layer and the solid electrolyte layer (solid electrolyte layer 4).

<Formation of laminated electrode body>
A negatively charged sulfide-based solid electrolyte material is injected from the injection device into the inner peripheral surface of the ulcer hole on which the negative electrode layer and the solid electrolyte layer 4 are formed, and the solid electrolyte material is applied to the inner peripheral surface of the ulcer hole charged to the opposite polarity. Was adhered to form a solid electrolyte layer (solid electrolyte layer 5).

Next, the ratio of lithium cobalt oxide powder having an average particle size of 5 μm: 70 parts by mass, carbon nanotubes: 4 parts by mass, and sulfide-based solid electrolyte (Li ₆ PS ₅ Cl) having an average particle size of 3 μm: 26 parts by mass. The mixture was mixed to prepare a positive electrode mixture. The positive electrode mixture was set in a hopper, and the positive electrode mixture was filled inside a mortar having a solid electrolyte material attached to the inner peripheral surface to form a laminated electrode body.

Further, the laminated electrode body was pressed with an upper punch to prepare a molded body of the laminated electrode body. The thicknesses of the negative electrode layer, the positive electrode layer, the solid electrolyte layer 4 and the solid electrolyte layer 5 of the laminated electrode body were confirmed by observing the cross section with an electron microscope. The thickness of the negative electrode layer was 1.3 mm, the thickness of the positive electrode layer was 0.7 mm, the thickness of the solid electrolyte layer 4 was 25 μm, and the thickness of the solid electrolyte layer 5 was 20 μm.

(Comparative Example 1)
The negative electrode mixture prepared in Example 1 (129 mg) was placed in a powder molding die having a diameter of 8 mm and pressure-molded using a press to form a negative electrode layer. Next, 2 mg of a sulfide-based solid electrolyte material (Li ₆ PS ₅ Cl) was charged onto the upper surface of the negative electrode layer and pressure-molded to form a solid electrolyte layer on the upper surface of the negative electrode layer. Further, 92 mg of the positive electrode mixture prepared in Example 1 was put into the upper surface of the solid electrolyte layer and pressure-molded to prepare a molded body of a laminated electrode body. The thickness of the negative electrode layer of the laminated electrode body was 1.3 mm, and the thickness of the positive electrode layer was 0.7 mm. On the other hand, the thickness of the solid electrolyte layer was non-uniform, and there were some places where the negative electrode layer and the positive electrode layer were in contact with each other and short-circuited.

(Comparative Example 2)
The negative electrode mixture prepared in Example 1 (129 mg) was placed in a powder molding die having a diameter of 8 mm and pressure-molded using a press to form a negative electrode layer. Next, 16 mg of a sulfide-based solid electrolyte (Li ₆ PS ₅ Cl) was charged onto the upper surface of the negative electrode layer and pressure-molded to form a solid electrolyte layer on the upper surface of the negative electrode layer. Further, 92 mg of the positive electrode mixture prepared in Example 1 was put into the upper surface of the solid electrolyte layer and pressure-molded to prepare a molded body of a laminated electrode body. The thickness of the negative electrode layer of the laminated electrode body was 1.3 mm, the thickness of the positive electrode layer was 0.7 mm, and the thickness of the solid electrolyte layer was 0.2 mm.

In the laminated electrode body of Example 1 produced by the production method of the present invention using a charged solid electrolyte material, both the solid electrolyte layer 4 and the solid electrolyte layer 5 could be formed with a thin and uniform thickness. On the other hand, in the laminated electrode body of the comparative example produced by the conventional method, the thickness of the laminated electrode body of the comparative example 1 in which the solid electrolyte layer was to be formed thinly became non-uniform, and the insulation between the negative electrode layer and the positive electrode layer was increased. The problem of inadequacy arose.

Next, the laminated electrode bodies of Example 1 and Comparative Example 2 were combined with a stainless steel outer can and a sealing can in a state where collectors made of expanded graphite sheets were arranged on the negative electrode layer side and the positive electrode layer side, respectively. , A coin-shaped battery was assembled by encapsulating it in a battery container composed of a gasket made of polyphenylene sulfide resin. The laminated electrode body of Example 1 was arranged so that the difference between the thickness of the laminated electrode body of Example 1 (2.025 mm) and the thickness of the laminated electrode body of Comparative Example 2 (2.2 mm) could be eliminated. The thickness of the expanded graphite sheet was made 0.18 mm thicker in total than that of Comparative Example 2.

A flat battery containing the laminated electrode body of Example 1 and a flat battery containing the laminated electrode body of Comparative Example 2 are assembled 10 by 10 each, charged and discharged, the discharge capacity is confirmed, and an internal short circuit occurs. I checked for the presence of. As a result, in the flat battery containing the laminated electrode body of Example 1, a short circuit could not be recognized in all ten of them. On the other hand, in the flat battery containing the laminated electrode body of Comparative Example 2, a short circuit was observed in 9 out of 10. That is, in the flat battery containing the laminated electrode body of Comparative Example 2, defects due to short circuits occurred at a rate of 90%.

This is because in the flat battery containing the laminated electrode body of Example 1, the solid electrolyte layer 5 formed on the peripheral side surface of the positive electrode layer can prevent the positive electrode layer from falling off, and the laminated electrode body of Comparative Example 2 is housed. In the flat battery, the solid electrolyte layer is not formed on the peripheral side surface of the positive electrode layer, which is caused by the positive electrode layer falling off.

1 Laminated electrode body, 2 Positive electrode layer, 3 Negative electrode layer, 4 Solid electrolyte layer, 5 Solid electrolyte layer, 6 Solid electrolyte layer 10 All-solid-state battery, 20 Exterior can, 21 Bottom, 22 Peripheral wall, 30 Seal can, 31 Flat surface , 32 Peripheral wall, 40 gasket 100 pressurizing device, 101 die, 101a mortar, 102 lower punch, 103 upper punch, 104 injection device, 105 lower punch, X electrode material, Y electrode material, W solid electrolyte material

Claims (9)

The first electrode layer, which is one of the positive electrode layer and the negative electrode layer,
The other second electrode layer of the positive electrode layer and the negative electrode layer,
A first solid electrolyte layer arranged between the first electrode layer and the second electrode layer,
A second solid electrolyte layer extending from the peripheral end of the first solid electrolyte layer along at least one peripheral side surface of the first electrode layer and the second electrode layer is provided.
The first solid electrolyte layer has a thickness t1 of 5 to 180 μm.
The second solid electrolyte layer is a laminated electrode body having a thickness t2 of 1 to 180 μm. The laminated electrode body according to claim 1.
A laminated electrode body in which the ratio (t1 / t3) of the thickness t1 of the first solid electrolyte layer to the thickness t3 of the positive electrode layer is 0.03 or more. The laminated electrode body according to claim 2.
A laminated electrode body in which the ratio (t1 / t3) of the thickness t1 of the first solid electrolyte layer to the thickness t3 of the positive electrode layer is 0.3 or less. The laminated electrode body according to any one of claims 1 to 3.
The second solid electrolyte layer extends along the peripheral side surface of the positive electrode layer.
The peripheral side surface of the negative electrode layer is an exposed laminated electrode body. Battery container and
An all-solid-state battery comprising the laminated electrode body according to any one of claims 1 to 4 housed in an internal space of a battery container. A die having a mortar that penetrates up and down, a lower pestle that is inserted from below the mortar and slides in the mortar, and an upper pestle that is inserted from above the mortar and slides in the mortar. And the process of preparing a pressurizing device
A step of forming one of the positive electrode layer and the negative electrode layer by filling the mortar hole with a first electrode material in a state where the opening below the mortar hole is closed by the lower pestle.
By adhering a solid electrolyte material from above the ulcer to the upper surface of the first electrode layer and the inner peripheral surface of the ulcer, a first solid electrolyte layer is formed on the upper surface of the first electrode layer. The process of forming the second solid electrolyte layer on the inner peripheral surface of the acetabulum,
A step of forming the other second electrode layer of the positive electrode layer and the negative electrode layer by filling the space surrounded by the first solid electrolyte layer and the second solid electrolyte layer with the second electrode material.
A step of forming a laminated electrode body by pressurizing the first electrode layer, the second electrode layer, the first solid electrolyte layer, and the second solid electrolyte layer with the lower and upper punches.
A method for manufacturing a laminated electrode body, which comprises a step of taking out the laminated electrode body from the mortar hole by relatively moving at least one of the upper and lower punches and the die. The method for manufacturing a laminated electrode body according to claim 6, further
The step of forming the first electrode layer by filling the mortar with the first electrode material and then pressurizing the first electrode layer with an upper and lower pestle before attaching the solid electrolyte material is included. , Manufacturing method of laminated electrode body. The method for manufacturing a laminated electrode body according to claim 6.
In the step of forming the first solid electrolyte layer and the second solid electrolyte layer, a solid electrolyte material is previously attached to the lower surface of the upper punch facing the upper surface of the first electrode layer, and the upper punch is attached to the first electrode layer. A first solid electrolyte layer is formed on the upper surface of the first electrode layer by moving it toward the upper surface and pressurizing it, and then a solid electrolyte material is adhered to the inner peripheral surface of the molar hole to form a second solid. A method for manufacturing a laminated electrode body that forms an electrolyte layer. The method for manufacturing a laminated electrode body according to claim 6, further
Before filling the mortar with the first electrode material, a solid electrolyte material is attached to the inner peripheral surface of the mortar in a state where the opening below the mortar is closed by the first lower punch. A step of forming a second solid electrolyte layer on the one electrode layer side and forming a third solid electrolyte layer on the upper surface of the first lower punch.
The first lower pestle together with the third solid electrolyte layer is removed from below the mortar, and the second lower pestle is inserted from below the mortar so as to be in contact with the lower end of the second solid electrolyte layer on the first electrode layer side. Including the process of
In the step of filling the mortar with the first electrode material, the space surrounded by the second solid electrolyte layer on the inner peripheral surface of the mortar and the upper surface of the second lower punch is filled with the first electrode material. , The first electrode layer is formed,
Before forming the first solid electrolyte layer and the second solid electrolyte layer on the side of the second electrode layer, the solid electrolyte material is adhered to the inner peripheral surface of the molar hole and the upper surface of the first electrode layer. A method for manufacturing a laminated electrode body, which comprises a step of forming a space in a molar hole.

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