JP2014222564A - All-solid battery, manufacturing method of all-solid battery and manufacturing device for all-solid battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of an all-solid battery of which the internal short-circuiting is unlikely to occur regardless of a difference in thickness of layers caused by thinning and capacity increase.SOLUTION: A manufacturing method of an all-solid battery includes the steps of: forming a first electrode layer 4 in a first composite collector member 1 on a surface of a first collector member 1a and inside of a first insulation member 1b, forming a solid electrolyte layer 5 on a surface of the first electrode layer 4 and then further forming a second electrode mixture layer 6; and disposing an adhesive layer 8 in a second insulation member 2b of a second composite collector member 2. The first insulation member 1b opposes the adhesive layer 8 disposed in the second insulation member 2b and in the state where the second insulation member 2b is positioned around the second electrode mixture layer 6, the second collector member 2a is pressed and deformed along a surface shape of the second electrode mixture layer 6 by an elastic member 31. The first insulation member 1b and the second insulation member 2b are then adhered by the adhesive layer 8.

Description

  The present invention relates to an all-solid battery, an all-solid battery manufacturing method, and an all-solid battery manufacturing apparatus.

  In order to achieve high performance and high capacity, all solid lithium ion secondary batteries have been attempted to be thin and large (see, for example, Patent Document 1). Patent Document 1 discloses a method for thinning and increasing the size of a battery by spraying a mixed powder material of an active material and a solid electrolyte charged with electric charge on the surface of a current collector with a carrier gas. .

JP 2011-1224028 A

  However, in such a conventional method, after the film is formed, when the film is pressed and solidified, the solid electrolyte layer is thinned for thinning or the electrode layer is thickened for high capacity. There is a problem that the internal structure of the all-solid-state battery is partially broken due to the difference in the thickness of each layer due to the fact that the internal short circuit easily occurs.

  Therefore, in view of the above problems, the present invention has an object to provide an all-solid-state battery that is not easily short-circuited internally, regardless of the difference in thickness of each layer that occurs due to thinning and high capacity, a manufacturing method thereof, and a manufacturing apparatus thereof. To do.

The all-solid-state battery of the present invention includes a first composite current collecting member comprising a thin plate-like first current collecting member and a thin plate-like first insulating member bonded to a peripheral portion of the surface of the first current collecting member, A positive electrode or negative electrode first electrode layer comprising a first composite current collecting member and a first electrode mixture layer laminated on the surface of the first current collecting member and inward of the first insulating member;
A solid electrolyte layer;
A second composite current collecting member composed of a thin plate-like second current collecting member and a thin plate-like second insulating member bonded to a peripheral portion of the surface of the second current collecting member; the second composite current collecting member; A second electrode layer of a negative electrode or a positive electrode comprising a second electrode mixture layer laminated on the surface of the second current collecting member and inward of the second insulating member,
When the solid electrolyte layer is disposed between the first and second electrode mixture layers and the first and second electrode layers are laminated with the insulating members facing each other, the first insulating member and the second insulating member are stacked. An adhesive layer is interposed between the insulating members and pressed by the pressing member via the elastic member so that no gap is generated between the second current collecting member, each electrode mixture layer and the solid electrolyte layer. It is characterized by that.

  It is preferable that at least one side surface of each electrode mixture layer is inclined with respect to the thickness direction of the layer, and the inclination angle of the side surface is more preferably 10 to 60 ° with respect to the layer surface direction of each layer, More preferably, the surface of the solid electrolyte layer has a larger area than the surface of each electrode layer.

The method for producing an all-solid battery according to the present invention is the above-described method for producing an all-solid battery, wherein the first composite current collecting member is first on the surface of the first current collecting member and more inward than the first insulating member. A step of laminating electrode mixture powder to form a first electrode layer;
Forming a solid electrolyte layer by laminating solid electrolyte powder on the surface of the first electrode layer, and further laminating powder of the second electrode mixture to form a second electrode mixture layer;
Providing an adhesive layer on the second insulating member of the second composite current collecting member,
Further, the first insulating member and the adhesive layer disposed on the second insulating member are arranged so as to face each other, and the second insulating member is positioned around the second electrode mixture layer so,
The second current collecting member is pressed and deformed along the surface shape of the second electrode mixture layer by the pressing member via the elastic member, and the first insulating member and the second insulating member are bonded by the adhesive layer. It is made to adhere.

An apparatus for producing an all-solid battery according to the present invention is the apparatus for producing an all-solid battery described above, comprising a first electrode layer having a first insulating member, a solid electrolyte layer, and a second electrode mixture of a second electrode layer. A cradle for supporting the main laminate;
A movable support member capable of supporting a sub-layered body composed of an adhesive layer provided on the second composite current collecting member and the second insulating member and disposed above the cradle and movably provided in the vertical direction; ,
A pressing member disposed above the movable support member and provided with an elastic member at the lower end;
When forming the all-solid battery by laminating and pressing the sub-laminate supported by the movable support member on the main laminate supported by the cradle,
After contacting the sub-laminate supported by the movable support member and the main laminate supported by the cradle by moving the pressing member downward and / or the cradle upward, By moving the pressing member downward and / or the cradle upward, the second insulating member is positioned around the second electrode mixture layer via the elastic member, The second current collecting member is deformed along the surface of the second electrode mixture layer, and the first insulating member and the second insulating member are bonded to each other by the adhesive layer. .

  According to the all-solid battery, the all-solid battery manufacturing apparatus, and the all-solid battery manufacturing method of the present invention, when pressing the all-solid battery, only the pressing member is pressed by pressing it through a deformable elastic member. Compared with the case of using, the shape of the elastic member changes with compression, and the current collecting member can be deformed and arranged along the surface shape of the electrode mixture layer, so that each electrode mixture layer and solid electrolyte It is possible to obtain a molded body having no gaps between the layers and the current collecting members. In addition, by providing an adhesive layer between the first insulating member and the second insulating member, it is possible to reliably maintain a pressed state in which the gaps between the respective layers are reduced, thereby suppressing an internal short circuit of the all-solid-state battery. Is done.

It is sectional drawing which shows schematic structure of the all-solid-state battery which concerns on this Embodiment. It is a perspective view of the manufacturing apparatus of the all-solid-state battery which concerns on this Embodiment. It is a principal part notched front view of the manufacturing apparatus of the all-solid-state battery. It is a side view of the manufacturing apparatus of the all-solid-state battery. It is AA sectional drawing of the manufacturing apparatus of the all-solid-state battery. It is BB sectional drawing of the manufacturing apparatus of the all-solid-state battery. It is sectional drawing explaining the manufacturing method of the all-solid-state battery which concerns on this Embodiment.

Hereinafter, an all-solid-state battery according to an embodiment of the present invention, a manufacturing method thereof, and a manufacturing apparatus thereof will be described.
In the following embodiments, the configuration of an all-solid battery will be described first, and then the manufacturing apparatus and manufacturing method will be described.
<All solid battery>
As shown in FIG. 1, the all solid state battery according to the present embodiment includes a thin plate-like first current collecting member 1a and a thin plate-like first insulating member bonded to the peripheral portion of the surface of the first current collecting member 1a. A first composite current collecting member 1 made of 1b, and a first electrode mixture layer 3 laminated on the surfaces of the first composite current collection member 1 and the first current collection member 1a and inward of the first insulating member 1b. A first electrode layer 4 of a positive electrode or a negative electrode, a solid electrolyte layer 5, a thin plate-like second current collecting member 2a, and a thin plate-like second electrode bonded to the peripheral portion of the surface of the second current collecting member 2a. Second composite current collecting member 2 composed of insulating member 2b, and second electrode composite material laminated on the surface of second composite current collecting member 2 and second current collecting member 2a and inward of second insulating member 2b A negative electrode or a positive electrode second electrode layer 7 comprising a layer 6, and a solid electrolyte layer 5 is disposed between the first and second electrode mixture layers 3, 6. When the first and second electrode layers 4 and 7 are laminated with the insulating members 1b and 2b facing each other, the adhesive layer 8 is interposed between the first insulating member 1b and the second insulating member 2b, and the elastic member By pressing with a pressing member via the, a gap is prevented from being generated between the second current collecting member 2 a, the electrode mixture layers 3, 6 and the solid electrolyte layer 5.

  Hereinafter, a more specific all solid state battery will be described. The case where the positive electrode layer is disposed as the first electrode layer 4 on the lower side will be described, and the case where the shape in plan view is a square will be described.

  As shown in FIG. 1, the all solid state battery according to the present embodiment includes a first electrode layer 4 that functions as a positive electrode, a solid electrolyte layer 5 that is stacked on the first electrode layer 4, and a stack on the solid electrolyte layer 5. And the second electrode layer 7 functioning as a negative electrode.

  Since the first electrode layer 4 and the second electrode layer 7 have the same configuration, they will be described as electrode layers 4 and 7 below. The electrode layers 4 and 7 are composed of thin plate-like current collecting members 1b and 2b and composite current collecting members 1 and 2 composed of thin plate-like insulating members 1b and 2b bonded to the periphery of the surface of the current collecting members 1a and 2a. The electrode collector layers 3 and 6 are laminated on the surfaces of the composite current collecting members 1 and 2 and the current collecting members 1a and 2a and inward of the insulating members 1b and 2b. In other words, openings 9 and 10 through which the current collecting members 1a and 2a are exposed are formed at the center of the composite current collecting members 1 and 2.

  A first insulating member 1b is disposed around the upper surface of a first current collecting member (also referred to as a positive current collecting member) 1a with a predetermined width through an adhesive 1c, and a first composite current collecting member (positive electrode current collecting member). 1), and a first electrode mixture layer (also referred to as a positive electrode mixture layer) 3 is disposed in an opening 9 formed in the central portion of the first composite current collection member 1. The first electrode layer 4 is configured.

  Then, solid electrolyte powder is laminated on the upper surface of the first electrode mixture layer 3 in the first electrode layer 4 so as to cover the entire first electrode mixture layer 3, and the solid electrolyte layer 5 A second electrode mixture layer (also referred to as a negative electrode mixture layer) 6 is laminated on the upper surface. Here, hereinafter, the first electrode mixture layer 3, the solid electrolyte layer 5, and the second electrode mixture layer 6 may be collectively referred to as a powder layer.

  In the all solid state battery according to the present embodiment, the adhesive 2c has a predetermined width on the upper surface of the second electrode mixture layer 6 and on the periphery of the upper surface of the second current collecting member (also referred to as negative electrode current collecting member) 2a. In a state where a second composite current collector member (also referred to as a negative electrode composite current collector member) 2 in which the second insulating member 2b is arranged via the first insulating member 1b and the second insulating member is pressed from above. The member 2b is firmly bonded via the adhesive layer 8.

  At this time, as shown in FIG. 1, the second current collecting member 2 a is in contact with the upper surface of the first insulating member 1 b outside the periphery of the solid electrolyte layer 5, and the first electrode mixture layer 3 and the second electrode An internal short circuit with the composite material layer 6 is prevented.

  Here, the shape of the all-solid battery in plan view will be described. The current collecting members 1a and 2a and the electrode mixture layers 3 and 6 are square, and of course, the adhesives 1c and 2c and the adhesive layer 8 are used. Since it is arranged along the side of the square, it has an opening at the center. For the adhesives 1c and 2c and the adhesive layer 8, a commonly used adhesion method may be used, or heat fusion may be substituted. In this embodiment, a pressure-sensitive adhesive is used for bonding.

  The respective sizes will be described. Since the second electrode layer 7 of the negative electrode (or positive electrode) is pressed and laminated above the first electrode layer 4 of the positive electrode (or negative electrode), each electrode mixture layer 3 , 6, the size of the current collecting members 1 a, 2 a, the internal dimensions of the insulating members 1 b, 2 b arranged around the current collecting members 1 a, 2 a, that is, the openings 9 provided in the insulating members 1 b, 2 b, The size of 10 is as follows.

  That is, as shown in FIG. 1, the opening 9 of the first insulating member 1 b is not less than the size of the first electrode mixture layer 3 of the first electrode layer 4 and the first electrode mixture layer 3. The solid electrolyte layer 5 disposed above is larger than the size of the opening 9 of the first insulating member 1b, and the second electrode mixture layer 6 of the second electrode layer 7 laminated thereon is a solid electrolyte layer. And the opening 10 of the second insulating member 2b disposed around the second electrode mixture layer 6 is not less than the size of the second electrode mixture layer 6 and is The size is such that the peripheral portion of the two current collecting members 2a is in contact with the first insulating member 1b.

The magnitude relationship is as follows.
The width L1 of one side of the first electrode mixture layer 3 ≦ the width L2 of one side of the opening 9 of the first insulating member 1b ≦ the width L3 of one side of the second electrode mixture layer 6 ≦ the width L4 of one side of the solid electrolyte layer 5 ≦ Width L5 of one side of the opening 10 of the second insulating member 2b
From the viewpoint of reducing the weight of the all-solid-state battery, the current collecting members 1a and 2a have a thickness of 10 to 50 μm, the first and second insulating members 1b and 2b have a thickness of 20 to 100 μm, and the adhesive layer 8 The total thickness of the electrode mixture layers 3 and 6 and the solid electrolyte layer 5 is larger than the total thickness of the insulating members 1b and 2b and the adhesive layer 8. Is preferred.

Furthermore, in the present embodiment, one side of the opening 9 of the first composite current collecting member 1 against a pressure of 7.35 to 14.7 MPa (75 to 150 kgf / cm ² ) that is preferable for pressurization during molding. The width is preferably 10 to 500 mm, and most preferably 50 mm. Note that the appropriate pressure range in the present embodiment is a numerical range in which a general elastic member can withstand pressure. Accordingly, the pressure is not limited to the above range as long as it is within the pressure range in which the elastic member can withstand pressure.

  In the present embodiment, no gap is formed between the second current collecting member 2a, the electrode mixture layers 3 and 6, and the solid electrolyte layer 5. In this configuration, the solid electrolyte layer 5 is disposed between the first and second electrode mixture layers 3 and 6, and the first and second electrode layers 4 and 7 are laminated with the insulating members 1b and 2b facing each other. In doing so, the adhesive layer 8 may be interposed between the first insulating member 1b and the second insulating member 2b, and may be pressed by a pressing member via an elastic member.

  According to this configuration, when all-solid-state batteries are pressurized, pressing is performed via a deformable elastic member (described later), and therefore, as compared with the case where only the pressing member (described later) is used, the compression is accompanied. Since the shape of the elastic member changes and the current collecting members 1a and 2a can be deformed and arranged along the surface shape of each electrode mixture layer 3 and 6, each electrode mixture layer 3 and 6 and solid It is possible to obtain a molded body having no gap between the electrolyte layer 5 and the current collecting members 1a and 2a. Further, by providing the adhesive layer 8 between the first insulating member 1b and the second insulating member 2b, it is possible to reliably maintain a pressed state in which the gaps between the respective layers are reduced. Short circuit is suppressed.

  And at least one side surface of each electrode compound-material layer 3 and 6 inclines with respect to the thickness direction. More specifically, at least one side surface of each electrode mixture layer 3, 6 is inclined within a range of 10 to 60 ° with respect to the layer surface (surface orthogonal to the layer thickness direction). It is preferable. According to this configuration, since a sudden change (discontinuous state) in the thickness of each layer in the powder layer is eliminated, occurrence of a fault due to internal stress generated in the molded body at the time of pressing is suppressed. Can be suppressed. In addition, since each electrode compound-material layer 3 and 6 is comprised with powder, it has an unevenness | corrugation in a layer surface and a side surface in many cases. In that case, the said inclination | tilt angle calculates | requires each plane based on the average value of an unevenness | corrugation about each electrode compound-material layer 3 and 6, respectively, measures the angle which they comprise, and each electrode compound-material layer 3 and 6 , The angle formed by the side surfaces and the layer surfaces in a plurality of cross sections may be measured, and the average value thereof may be calculated. Therefore, at least one side surface of each electrode mixture layer 3, 6 is inclined in an average range of 10 to 60 ° with respect to the layer surface direction of each electrode mixture layer 3, 6.

  The surface of the solid electrolyte layer 5 is preferably larger in area than the surfaces of the electrode mixture layers 3 and 6. With this configuration, contact between the positive electrode mixture layer 3 and the negative electrode mixture layer 6 on the side surface of the powder layer is avoided, so that an internal short circuit can be suppressed.

  Furthermore, it is preferable to use an elastic member having a larger area than the current collecting members 1a and 2a. According to this configuration, the elastic member is deformed so as to cover the side surface of each layer by pressing, so that the current collecting members 1 a and 2 a are deformed along the surface shapes of the electrode mixture layers 3 and 6 and the solid electrolyte layer 5. At the same time, a molded body without voids is obtained between the electrode mixture layers 3 and 6 and the solid electrolyte layer 5 and the current collecting members 1a and 2a, and the collapse of the powder layer can be suppressed.

Hereinafter, the function of each layer of the all-solid-state battery and the materials used will be described.
As current collecting members 1a and 2a, copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al ), Germanium (Ge), indium (In), lithium (Li), tin (Sn), or an alloy thereof or the like. In the present embodiment, an aluminum foil is employed as the positive electrode current collecting member 1a, and a copper foil is employed as the negative electrode current collecting member 2a.

  The electrode mixture layers 3 and 6 are made of a mixed material in which an electrode active material that secures an electron conduction path between particles and a sulfide-based inorganic solid electrolyte are mixed at a predetermined ratio in order to perform an oxidation-reduction reaction for sending and receiving electrons. It is a layer. In the present embodiment, a lithium ion conductive solid electrolyte is used as the sulfide-based inorganic solid electrolyte. Thus, by mixing a lithium ion conductive solid electrolyte with the electrode active material, ion conductivity can be imparted in addition to electron conductivity, and an ion conduction path can be secured between the particles.

The positive electrode active material suitable for the positive electrode mixture layer 3 is not particularly limited as long as it can insert and desorb lithium ions. For example, lithium-nickel composite oxide (LiNi _x M _1-x O ₂ , where M is at least one of Co, Al, Mn, V, Cr, Mg, Ca, Ti, Zr, Nb, Mo and W Elements), layered oxides such as lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), lithium manganate (LiMn ₂ O ₄ ), lithium iron phosphate (LiFePO ₄ ) having an olivine structure, spinel structure A solid solution such as lithium manganate (LiMn ₂ O ₄ , Li ₂ MnO ₃ , LiMO ₂ ) or a mixture thereof, or a sulfide such as sulfur (S) or lithium sulfide (Li ₂ S) can also be used. In the present embodiment, as the positive electrode active material, specifically, a lithium / nickel / cobalt / aluminum composite oxide (LiNi _0.8 Co _0.15 Al _0.05 O ₂ , hereinafter referred to as an NCA-based composite oxide) Are sometimes used).

On the other hand, examples of the negative electrode active material suitable for the negative electrode mixture layer 6 include materials that are compounded with sulfide-based inorganic solid electrolytes in addition to carbon materials such as natural graphite, artificial graphite, graphite carbon fiber, and resin-fired carbon. If it is, it will not be limited. For example, a metal oxide such as lithium titanate (Li ₄ Ti ₅ O ₁₂ ) can also be used. In this embodiment, natural or artificial graphite is employed.

Further, on the surfaces of the positive electrode active material and the negative electrode active material, zirconia (ZrO ₂ ), alumina (Al ₂ O ₃ ), lithium titanate (Li ₄ Ti ₅ O ₁₂ ), lithium niobate (LiNbO ₃ ), carbon (C ) Etc. can be used as each electrode active material.

As the lithium ion conductive solid electrolyte, a material composed of an organic compound or an inorganic compound, or a mixture of an organic and an inorganic compound can be used, and those known in the field of lithium ion batteries can be used. In the present embodiment, it is known that the sulfide-based inorganic solid electrolyte has higher ionic conductivity than other inorganic compounds, and therefore a sulfide-based inorganic solid electrolyte is employed. Specifically, Li ₂ S—P ₂ S ₅ system, Li ₂ S—GeS ₂ system, Li ₂ S—Ge ₂ S ₂ system, Li ₂ S—GeS ₂ —P ₂ S ₅ system, Li ₂ S— Examples thereof include glass ceramics such as GeS ₂ —ZnS and Li ₂ S—SiS ₂ . In the present embodiment, Li ₂ S—P ₂ S ₅ glass ceramics is employed.

In the present embodiment, the material of the solid electrolyte layer 5 is not particularly limited, and a material composed of an organic compound or an inorganic compound, or a mixture of an organic and an inorganic compound can be used. A well-known thing can be used. In the present embodiment, it is known that the sulfide-based inorganic solid electrolyte has higher ionic conductivity than other inorganic compounds, and therefore a sulfide-based inorganic solid electrolyte is employed. Specifically, Li ₂ S—P ₂ S ₅ system, Li ₂ S—GeS ₂ system, Li ₂ S—Ge ₂ S ₂ system, Li ₂ S—GeS ₂ —P ₂ S ₅ system, Li ₂ S— Examples thereof include glass ceramics such as GeS ₂ —ZnS and Li ₂ S—SiS ₂ . In the present embodiment, Li ₂ S—P ₂ S ₅ glass ceramics is employed.
<All-solid battery manufacturing equipment>
Embodiments of an all-solid battery manufacturing apparatus according to the present invention will be described with reference to FIGS.

  As shown in FIG. 2, the manufacturing apparatus is roughly divided into an apparatus main body (holding apparatus) 20 for holding the constituent members (pressed members) of the all-solid-state battery and performing the function of the mold, and the apparatus. It is comprised from the press (it can also be said a press) 40 for pressing the structural member hold | maintained at the main body 20 and shape | molding an all-solid-state battery.

  As shown in FIGS. 2 and 3, the pressing device 40 includes a base portion 41 on which the constituent members of the all-solid-state battery can be placed, and a pair of left and right support members 42 above the base portion 41. And a pushing tool 45 that is provided on the crown portion 43 and protrudes downward by a hydraulic cylinder (an example of a pressurizing device) 44.

  The apparatus main body 20 is disposed in a support base 21 disposed on the upper surface of the base portion 41 of the pressing machine 40 and a concave portion 21a formed in the center of the support base 21 and is a constituent member of an all-solid battery ( For example, a receiving base 22 having a mounting surface S on which a first electrode layer 4, a solid electrolyte layer 5, and a second electrode mixture layer 6 can be mounted (actually, a lower movable member described later) The component members of the all-solid-state battery are also placed on the members), and the two first support members (both support bolts) provided at the four corners of the support base 21 and erected on one diagonal line 23) and two second strut members 24 (also referred to as strut bolts) 24, which are erected on the other diagonal line different from these two first strut members 23 and shorter than the first strut members 23, The support table 21 is arranged with a predetermined height via two first support members 23. The fixed plate 25 and the two first support members 23 erected on the support 21 are guided so as to be movable in the vertical direction and coil springs 26 are externally fitted to the first support members 23. Is moved in the vertical direction to the plate-like upper movable member 27 that is urged upward by the two, and to the two second support members 24 erected on the support base 21 as shown in FIGS. A plate-like lower movable member 29 provided with an opening 29a that can be guided and urged upward by pin-like urging tools 28 provided on the left and right sides and can guide the cradle 22 in the vertical direction. And a pressing member 33 detachably provided with a mounting body 32 held by the upper movable member 27 by a pin-shaped holding member 30 and having an elastic member 31 attached to the lower end thereof. Here, examples of the elastic member 31 include natural rubber, synthetic rubber, and silicon rubber.

  Further, the lower movable member 29 has a high standby position (A) in which the pin-like urging tool 28 protrudes long as shown in FIG. 3, and a pin-like urging tool 28 as shown in FIG. It is possible to move up and down with a lower press preparation position (B) projecting about half, and a holding tool 34 for holding the press preparation position (B) is provided. As this holder 34, for example, it is provided on the pedestal 22 side via a horizontal pin 35 so as to be swingable (rotatable) in a vertical plane, and to an engagement pin 36 provided on the lower movable member 29. A detachable locking hook 37 is used (a configuration in which an engaging pin and a hook are used may be used). In FIG. 1, the holder 34 is not shown.

  Further, as shown in FIG. 5, the pressing member 33 is disposed in the opening 27a formed in the upper movable member 27 and is provided by the pin-shaped holding member 30 provided at a position different by 90 degrees in plan view. It is pressed from two directions and supported. According to this structure, it can replace | exchange for the press member 33 of appropriate hardness according to pressing force.

  Furthermore, a spherical body engaging portion 39 is provided at a connection portion between the pushing tool 45 and the pressing member 33. Specifically, as shown in FIGS. 3 and 4, a spherical body 39 a (hemisphere) is provided on the pressing member 33 side (lower side) of the pushing tool 45, and the pushing tool 45 side (upper side) of the pressing member 33 is provided. An engaging groove 39b having a concave curved surface is provided, and the spherical body 39a and the engaging groove 39b are engaged with each other. With this configuration, when a pressing force is applied to the pressing member 33, even if the lower surface of the pressing member 33 has a slight inclination on the surface of the constituent member that is a pressed material, the pressing member 33 follows the surface and is evenly applied to the surface of the constituent member. Has been added.

  Further, as shown in FIG. 6, an opening 29a capable of guiding the cradle 22 is formed at the center of the lower movable member 29, and a stepped guide portion having a wider width is formed around the opening 29a. 29b is formed so that the first composite current collecting member 1 can be guided and placed.

According to the manufacturing apparatus according to the present embodiment, when the all solid state battery is pressurized, the pressure is applied through the elastic member 31 that is deformable, so that compared with the case where only the pressing member 33 is used, the compression is accompanied. Since the shape of the elastic member 31 is changed and the current collecting members 1a and 2a can be deformed and arranged along the surface shape of the electrode mixture layers 3 and 6, the electrode mixture layers 3 and 6 and It is possible to obtain a molded body having no voids between the solid electrolyte layer 5 and the current collecting members 1a and 2a. Further, by providing the adhesive layer 8 between the first insulating member 1b and the second insulating member 2b, it is possible to reliably maintain a pressed state in which the gaps between the respective layers are reduced. Short circuit is suppressed.
<All-solid battery manufacturing method>
An embodiment of the method for producing an all solid state battery according to the present invention will be described with reference to FIG.

  In the present embodiment, the method for manufacturing an all-solid-state battery is as follows: the first composite current collecting member 1 is a powder of the first electrode mixture on the surface of the first current collecting member 1a and inward of the first insulating member 1b. And forming the first electrode layer 4, and forming the solid electrolyte layer 5 by laminating the solid electrolyte powder on the surface of the first electrode layer 4, and then further adding the powder of the second electrode mixture A step of laminating and forming the second electrode mixture layer 6; and a step of disposing the adhesive layer 8 on the second insulating member 2b of the second composite current collecting member 2. Furthermore, the first insulating member 1b and the second insulating member 2b are arranged so that the adhesive layer 8 is opposed to each other, and the second insulating member 2b is positioned around the second electrode mixture layer 6 Thus, the second current collecting member 2a is pressed and deformed along the surface shape of the second electrode mixture layer 6 by the pressing member 33 via the elastic member 31, and the first insulating member 1b and the second insulating member are deformed. 2b can be adhered by the adhesive layer 8.

  Specifically, first, the first and second composite current collecting members 1 and 2 are each assembled. The first and second composite current collecting members 1 and 2 have the same configuration. First and second insulating members 1b and 2b having openings 9 and 10 at the center along the periphery of the surfaces of the first and second current collecting members 1a and 2a are bonded by an adhesive or heat fusion. To do. That is, the first and second current collecting members 1 a and 2 a are exposed at the positions of the openings 9 and 10.

  The first electrode mixture layer 3 is formed by laminating the powder of the first electrode mixture in the opening 9 of the first composite current collecting member 1. That is, the solid electrolyte layer 5 is formed by laminating the solid electrolyte powder on the first current collecting member 1a. The second electrode composite material layer 6 is formed by laminating the powder of the second electrode composite material on the surface of the solid electrolyte layer 5. Hereinafter, for convenience, this laminate is referred to as a main laminate X.

On the other hand, the adhesive layer 8 is provided on the surface of the second insulating member 2b of the second composite current collecting member 2 (the surface on the side where the second current collecting member 1a is not adhered). Hereinafter, for convenience, this laminate is referred to as a sub laminate Y.
Next, the main laminate X and the sub laminate Y are bonded through the adhesive layer 8.

  That is, as shown in FIGS. 7A and 3, the main laminated body X is placed on the mounting surface S of the receiving table 22, the sub laminated body Y is placed on the lower movable support member 29, and the first insulating member It arrange | positions so that 1b and the contact bonding layer 8 arrange | positioned at the 2nd insulating member 2b may oppose.

  As shown in FIG. 7 (b), the sub laminate Y is brought close to the main laminate X by the pressing member 33 to which the pressing force is transmitted from the pushing tool 45 (not shown) of the pressing machine 40 (not shown). Press. Specifically, the pressing member 33 is lowered by lowering the pressing device 40, and the lower movable support member 29 is pushed down by lowering the elastic member 31. The current collecting member 2a is laminated in parallel with the main laminate X. When the pressing is continued, the air contained in the main laminate X is pushed out and the main laminate X is compressed.

  At this time, as shown in FIG. 7C, the pressing member 33 presses and deforms the second current collecting member 2 a along the surface shape of the second electrode mixture layer 6 via the elastic member 31. The second insulating member 2 b is positioned around the second electrode mixture layer 6. Specifically, when the pressure is continued, the air to be pushed out decreases, so that the bulk of the main laminate X becomes difficult to decrease, and the elastic member becomes the surface shape of the second electrode mixture layer 6 with the progress of pressing. The main laminate X is wrapped with the second current collecting member 2a by being deformed together. At the same time, the adhesive layer 8 provided on the second composite current collector 2 is pressed against the first composite current collector 1, and the composite current collectors 1 and 2 seal the powder layer.

Further, the first insulating member 1b and the second insulating member 2b are firmly bonded by pressing the adhesive layer 8 with the pressing member 33.
According to the manufacturing method according to the present embodiment, the second current collecting member 2a is deformed into the surface shape of the second electrode mixture layer 2 by deforming the second current collecting member 2a while applying pressure. By sealing the powder layer while extruding air inside the powder layer, an all-solid battery in which a void through which the powder flows can be hardly formed can be manufactured.

  In addition, according to this manufacturing method, when the all solid state battery is pressurized, the elastic member 31 is compressed with the compression by pressing the elastic member 31 via the deformable elastic member 31 as compared with the case where only the pressing member 33 is used. The current collecting members 1a and 2a can be deformed and arranged along the surface shape of the electrode mixture layers 3 and 6, so that the electrode mixture layers 3 and 6 and the solid electrolyte layer can be arranged. 5 and a molded body having no gap between them and each of the current collecting members 1a and 2a can be obtained. Further, by providing the adhesive layer 8 between the first insulating member 1b and the second insulating member 2b, it is possible to reliably maintain a pressed state in which the gaps between the respective layers are reduced. Short circuit is suppressed.

  And according to this manufacturing method, the operation | work which compresses each layer, expelling the air between particle | grains by pressing through the elastic member 31, and the 1st composite current collection member 1 and the 2nd composite current collection member 2 The sealing operation can be performed in one step. Furthermore, since the 1st composite current collection member 1 and the 2nd composite current collection member 2 are adhere | attached firmly by pressurizing the contact bonding layer 8, a powder layer can be packaged more reliably.

  Furthermore, when the above-mentioned all-solid-state battery is a single cell, the single cell has a collapse resistance as described above, so the single cell connection step such as the single cell stacking step or the composite sealing step with the support is performed. Even in work, internal short circuit due to collapse can be suppressed. As a result, the operability at the time of manufacture is improved and the yield is improved.

  Finally, the collapse of the molded product during production, which is a cause of internal short circuit in a general all solid state battery, will be described. This collapse is roughly divided into the following three patterns. According to the manufacturing method according to the present embodiment, it is possible to suppress the collapse of these first to third patterns.

  First, the first pattern will be described. The main laminate X has a thick central portion and a thin peripheral portion. If the sub-laminate Y is placed on the main laminate X and pressed using only a rigid pressing member without an elastic member, the pressing member 33 is maintained parallel to the current collecting members 1a and 2a. Therefore, the pressed pressure is applied only to the thick central portion. For this reason, the outer peripheral part of the powder layer becomes non-molded or insufficiently molded and becomes brittle. That is, the first pattern is that when some impact or the like is applied in the subsequent process, a fragile outer peripheral portion of the molded body is collapsed and an internal short circuit of the all solid state battery is generated. On the other hand, according to the present embodiment, when pressurizing the all solid state battery, pressing is performed through the deformable elastic member 31, thereby compressing the all solid state battery as compared with the case where only the pressing member 33 is used. Accordingly, the shape of the elastic member 31 is changed, and the current collecting members 1a and 2a can be deformed and arranged along the surface shape of the electrode mixture layers 3 and 6. It is possible to obtain a molded body in which the outer peripheral portion can be sufficiently molded without a gap between the electrolyte layer 5 and the current collecting members 1a and 2a.

  Next, the second pattern is one in which the powder is scattered by an air flow generated when the pressing speed at the time of manufacture is too high, and the molded body collapses. The airflow referred to here is generated when air between powder particles is pushed out of the powder layer by compression. On the other hand, according to the present embodiment, since the lowering of the pressing portion 33 is performed by hydraulic pressure, it becomes easy to control the pressurization speed, and the collapse due to the second pattern is suppressed.

  And as above-mentioned, in the powder layer of the main laminated body X, a 3rd pattern is that a fault arises in the part (discontinuous part) where the thickness of each layer changes suddenly. In particular, since the solid electrolyte layer 5 functions as an electrical insulating layer, an internal short circuit occurs when a fault occurs in the solid electrolyte layer 5. On the other hand, according to the present embodiment, since the elastic member is deformed along the surface shape of the powder layer when pressed by pressing with the pressing member via the elastic member, the thickness of the powder layer It is possible to prevent the pressing force applied by the difference between the two from becoming uneven. That is, since the elastic member 31 is deformed corresponding to the variation in the thickness of the main laminate X, the laminate X is evenly pressurized and the occurrence of a fault is suppressed. Further, even if the pressing is completed, the second composite current collecting member 2 is in close contact with the second electrode mixture layer 6 and the solid electrolyte layer 5, so that it is difficult to form a void in which air and particles can move. As a result, it is possible to manufacture an all-solid battery having a structure in which the outer peripheral portion of the molded body is prevented from collapsing and hardly collapses. In the present embodiment, by inclining the side surfaces of the electrode mixture layers 3 and 6, the sudden change (discontinuous state) of the thickness of each layer in the powder layer is eliminated, so that when pressing Since generation of a fault due to internal stress generated in the molded body is suppressed, an internal short circuit can also be suppressed.

As described above, according to the all-solid-state battery, the all-solid-state battery manufacturing method, and the all-solid-state battery manufacturing apparatus according to the present embodiment, each of the collapses according to the first to third patterns is solved. Can do.
[Modification]
Although the case where the positive electrode layer is disposed as the first electrode layer 4 on the lower side has been described in the present embodiment, the negative electrode layer may naturally be disposed as the first electrode layer 4 on the lower side.

  Moreover, in this Embodiment, although the planar view shape of the all-solid-state battery was illustrated as a square shape, it is not limited to this. For example, when the planar view shape is circular, the central openings 9 and 10 may also be circular. Moreover, you may make the planar view shape of an all-solid-state battery different from the planar view shape of the opening parts 9 and 10 of each insulation member 1b, 2b.

And in this Embodiment, although it was set as the structure which obtains a molded object by moving the press member 33 below, it is not limited to this. For example, it is good also as a structure which obtains a molded object by moving the cradle 22 upwards or moving the cradle 22 upwards, and moving the press member 33 below.
[Example]
Hereinafter, examples of the all solid state battery according to the present embodiment will be described.

  PET (polyethylene terephthalate) having a square with a side of 28 mm and a square with an opening 9 of a square with a side of 22 mm in the center and an aluminum foil (first current collector 1a) with a side of 28 mm and a thickness of 20 μm and a side of 40 mm. The positive electrode current collector 1 was prepared by bonding the first insulating member 1b made of) through a square pressure-sensitive adhesive 1c having a square opening of 22 mm on one side and a square of 26 mm on one side. A copper foil (second collector 2a) having a square of 40 mm on one side and a thickness of 10 μm, a square having an opening 10 having a square of 28 mm on one side in the center and a square of 50 mm on one side and having a thickness of 50 μm. 2 A negative electrode composite current collecting member 2 was prepared in which the insulating member 2b was bonded via a square pressure-sensitive adhesive 2c having a side having a side of 36 mm and a side having a side of 28 mm. Further, the negative electrode composite current collecting member 2 is provided with a pressure-sensitive adhesive layer (adhesive layer 8) used for adhesion to the positive electrode composite current collector 1 on the opposite surface of the second insulating member 2b to which the copper foil is adhered. Provided. This pressure-sensitive adhesive layer (adhesive layer 8) is a square having a side of 36 mm and an opening provided in the center thereof is a square having a side of 28 mm.

A Li ₂ S—P ₂ S ₅ -based glass ceramic as a solid electrolyte and an NCA-based composite oxide as a positive electrode active material were mixed at a weight ratio of 8: 2 to prepare a positive electrode mixture. And glass ceramics Li 2 _{S-P 2} S ₅ based anode active and graphite as material 7: a mixture of negative electrode mixture material was prepared in a weight ratio of 3.

  Then, 110 mg of the positive electrode mixture powder was formed (laminated) into a square shape having a side of 20 mm in the opening 9 of the positive electrode composite current collecting member 1 to form the positive electrode mixture layer 3. On the positive electrode mixture layer 3, 85 mg of solid electrolyte powder was formed (laminated) into a square shape with a side of 26 mm to form the solid electrolyte layer 5. On this solid electrolyte layer 5, 110 mg of the negative electrode composite powder was formed in a square shape with a side of 24 mm. In this way, the main laminate X was produced.

The main laminate X was placed on the mounting surface S of the receiving table 22, and the sub laminate Y was placed on the lower movable support member 29. A silicon rubber plate (elastic member 31) having a square shape with a side of 48 mm and a thickness of 5 mm was attached to the tip of the pressing member 33. Finally, it was pressed with a force of 2.94 × 10 ³ N (300 kgf) to produce a molded body.

The all-solid battery was sandwiched between two supports (a stainless plate having a side of 40 mm and a thickness of 0.3 mm), and vacuum-sealed with a heat-fusible laminate equipped with a tab for electrical extraction. At this time, electrical connection with the all-solid-state battery in the laminate was ensured by bringing the tab for electrical extraction into contact with the stainless steel plate as the support. The all-solid battery that was vacuum-sealed was pressurized with a force of 3.92 × 10 ⁵ N (40 ton) with a hydraulic press to obtain a finished battery. In addition, the process from preparation of an electrode compound material to vacuum sealing was performed in an environment with a dew point of −80 ° C. or lower.

When 10 all-solid-state batteries were produced in the above process, no internal short circuit occurred in all the all-solid-state batteries.
[Comparative Example 1]
For comparison, an elastic member 31 was not attached to the tip of the pressing member 33, and an all-solid battery was manufactured in the same manner and under the same conditions as in Example 1 except that. An internal short circuit occurred in 5 all solid batteries among the 10 all solid batteries produced. In the battery in which the internal short circuit has occurred, the adhesion between the negative electrode composite current collector member 2 and the positive electrode composite current collector member 1 is incomplete, and a gap is formed between the composite current collector members 1 and 2 of both electrodes at the outer periphery of the all-solid battery. It had been. Moreover, when these were disassembled, the outer periphery of the powder layer was missing.
[Comparative Example 2]
In addition, an all-solid battery was produced in the same manner and under the same conditions as in Example 1 except that the pressure-sensitive adhesive layer 8 for bonding the positive electrode composite current collector member 1 and the negative electrode composite current collector member 2 was not provided. Although it was pressed with a force of 2.94 × 10 ³ N (300 kgf), when the pressing was stopped, a gap was generated between the negative electrode composite current collector member 2 and the positive electrode composite current collector member 1. An internal short circuit occurred in 7 all solid batteries among the 10 all solid batteries produced. From the above, it is considered that an internal short circuit occurred in the process of vacuum sealing.

DESCRIPTION OF SYMBOLS 1 1st composite current collection member 1a 1st current collection member 1b 1st insulation member 1c adhesive material 2 2nd composite current collection member 2a 2nd current collection member 2b 2nd insulation member 2c adhesive material 3 1st electrode compound-material layer 4 1st electrode layer 5 Solid electrolyte layer 6 2nd electrode compound material layer 7 2nd electrode layer 8 Adhesive layer 9 Opening part 10 Opening part X Main laminated body Y Sub laminated body 20 Device main body 21 Supporting base 21a Concave part 22 Receiving base 23 First strut material 24 Second strut material 25 Fixed plate 26 Coil spring 27 Upper movable member 28 Pin-shaped biasing member 29 Lower movable member 29a Opening portion 30 Pin-shaped holder 31 Elastic member 32 Attachment body 33 Pressing member 34 Holding tool 35 Horizontal pin 36 Engagement pin 37 Hook for locking 38 Holding pin 39 Spherical body engaging part 39a Spherical body 39b Concave groove engaging groove 40 Pressing machine 41 Base part 42 Supporting part 43 Crown part 44 Sunda 45 pusher

Claims (6)

A first composite current collecting member comprising a thin plate-like first current collecting member and a thin plate-like first insulating member bonded to a peripheral portion of the surface of the first current collecting member, the first composite current collecting member, A positive electrode or negative electrode first electrode layer comprising a first electrode mixture layer laminated on the surface of the first current collecting member and inward of the first insulating member;
A solid electrolyte layer;
A second composite current collecting member composed of a thin plate-like second current collecting member and a thin plate-like second insulating member bonded to a peripheral portion of the surface of the second current collecting member; the second composite current collecting member; A second electrode layer of a negative electrode or a positive electrode comprising a second electrode mixture layer laminated on the surface of the second current collecting member and inward of the second insulating member,
When the solid electrolyte layer is disposed between the first and second electrode mixture layers and the first and second electrode layers are laminated with the insulating members facing each other, the first insulating member and the second insulating member are stacked. An adhesive layer is interposed between the insulating members and pressed by the pressing member via the elastic member so that no gap is generated between the second current collecting member, each electrode mixture layer and the solid electrolyte layer. All-solid-state battery characterized by being made.   The all-solid-state battery according to claim 1, wherein at least one side surface of each electrode mixture layer is inclined with respect to the thickness direction of the layer.   The all-solid-state battery according to claim 2, wherein an inclination angle of the side surface is 10 to 60 ° with respect to a layer surface direction of each layer.   The all-solid-state battery according to any one of claims 1 to 3, wherein the surface of the solid electrolyte layer has a larger area than the surface of each electrode layer. It is a manufacturing method of the all-solid-state battery as described in any one of Claims 1 thru | or 4, Comprising:
Forming a first electrode layer by laminating powder of the first electrode mixture on the surface of the first current collecting member and inward of the first insulating member on the first composite current collecting member;
Forming a solid electrolyte layer by laminating solid electrolyte powder on the surface of the first electrode layer, and further laminating powder of the second electrode mixture to form a second electrode mixture layer;
Providing an adhesive layer on the second insulating member of the second composite current collecting member,
Further, the first insulating member and the adhesive layer disposed on the second insulating member are arranged so as to face each other, and the second insulating member is positioned around the second electrode mixture layer so,
The second current collecting member is pressed and deformed along the surface shape of the second electrode mixture layer by the pressing member via the elastic member, and the first insulating member and the second insulating member are bonded by the adhesive layer. A method for producing an all-solid-state battery, comprising bonding. An apparatus for producing an all-solid battery according to any one of claims 1 to 4,
A cradle for supporting a main laminate comprising a first electrode layer having a first insulating member, a solid electrolyte layer, and a second electrode mixture of a second electrode layer;
A movable support member capable of supporting a sub-layered body composed of an adhesive layer provided on the second composite current collecting member and the second insulating member and disposed above the cradle and movably provided in the vertical direction; ,
A pressing member disposed above the movable support member and provided with an elastic member at the lower end;
When forming the all-solid battery by laminating and pressing the sub-laminate supported by the movable support member on the main laminate supported by the cradle,
After contacting the sub-laminate supported by the movable support member and the main laminate supported by the cradle by moving the pressing member downward and / or the cradle upward, By moving the pressing member downward and / or the cradle upward, the second insulating member is positioned around the second electrode mixture layer via the elastic member, The second current collecting member is deformed along the surface of the second electrode mixture layer, and the first insulating member and the second insulating member are bonded to each other by the adhesive layer. All-solid battery manufacturing equipment.

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