JP2008053125A - Fully solid electric storage element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fully solid electric storage element, in which the thickness of an electrolyte layer between electrodes can be reduced while increasing the contact area of the electrodes with electrolyte. <P>SOLUTION: The electric storage element comprises one or two or more units including a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a solid electrolyte interposed between the positive electrode and the negative electrode in contact thereto. The solid electrolyte in at least one of the units has a zigzag or alternate arrangement structure composed of at least part of the positive electrode and at least part of the negative electrode. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an all-solid-state energy storage device and a method for manufacturing the same.

In recent years, with the development of portable devices such as personal computers and mobile phones, the demand for batteries as power sources has been greatly expanded. In batteries used for such applications, liquid electrolytes (electrolytic solutions) such as organic solvents are conventionally used as a medium for moving ions. A battery using such an electrolytic solution may cause problems such as leakage of the electrolytic solution. In order to solve such a problem, development of an all-solid-state electric storage element in which a solid electrolyte is used in place of a liquid electrolyte and all other elements are made of solid is underway. Such an all-solid-state energy storage device has a solid electrolyte, so there is no fear of leakage that induces ignition and the like, and problems such as deterioration of battery performance due to corrosion hardly occur. As such an all solid lithium secondary battery, a battery using a lithium ion conductive electrolyte such as Li ₂ S—SiS ₂ —Li ₃ PO ₄ as a solid electrolyte is disclosed (for example, see Patent Document 1).

On the other hand, the all-solid-state energy storage device generally has a lower output than a battery using a liquid electrolyte, and it is difficult to extract a large current. In addition, the all-solid-state energy storage device has a problem in that rate characteristics and cycle characteristics in charge and discharge are low, and battery life is short as compared with a battery using a liquid electrolyte. A solid electrolyte battery in which an inorganic oxide made of the same material as that of the solid electrolyte is interposed between the particles of the electrode active material is disclosed in order to solve such problems and to take out a large current and improve charge / discharge cycle characteristics. (For example, refer to Patent Document 2). Further, it is disclosed that a secondary battery is formed by injecting a gel electrolyte between a positive electrode active material and a negative electrode active material having a large number of rod-shaped protrusions protruding toward opposite electrodes ( Non-patent document 1).
JP-A-5-205741 JP 2000-311710 A B. Dunn et al. Chem Rev., 104, 4463 (2004)

  However, even the all-solid-state energy storage device disclosed in Patent Document 2 still has room for improvement in terms of output characteristics and charge / discharge cycle characteristics. By the way, when the contact area between the electrode active material and the electrolyte is increased, the capacity is increased, and the ionic conductivity is improved as the electrolyte layer is thinner. In order to increase the contact area, when the interface between the electrode active material and the electrolyte is roughened or made porous and at the same time the electrolyte layer is made thin, there is a possibility that the positive electrode and the negative electrode are locally short-circuited. Further, in such a case, the structure is complicated, and the degree of freedom in electrical connection between cells tends to be low. In addition, the method according to Non-Patent Document 1 cannot be expected to improve ion conductivity by thinning the electrolyte layer.

  Accordingly, an object of the present invention is to provide an all-solid-state energy storage device capable of increasing the contact area between the electrode and the electrolyte body and simultaneously reducing the thickness of the electrolyte layer between the electrodes, and a method for manufacturing the same. . The present invention also provides an all-solid-state energy storage device capable of increasing the contact area between the electrode and the electrolyte body and reducing the thickness of the electrolyte body between the electrodes without complicating the structure, and a method for manufacturing the same. Another purpose is to do. Furthermore, the present invention can increase the contact area between the electrode and the electrolyte body and simultaneously reduce the thickness of the electrolyte body between the electrodes and improve the degree of freedom of electrical connection between the cells. Another object is to provide a solid state energy storage device and a method for manufacturing the same.

  As a result of examining the arrangement structure of the positive electrode, the negative electrode, and the solid electrolyte body, the present inventor has provided an arrangement structure in which a gel-like solid electrolyte body is interposed between the positive electrode and the negative electrode arranged alternately or in a staggered manner. The inventors have found that the above-described problems can be achieved, and have completed the present invention. That is, according to the present invention, the following means are provided.

  According to the present invention, comprising one or more units having a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a gelled solid electrolyte body in contact with the positive electrode and the negative electrode, In the solid electrolyte body in at least one of the units, there is provided an all-solid-state electric storage element having a staggered or alternating arrangement structure of at least a part of the positive electrode and at least a part of the negative electrode.

  In the all-solid-state energy storage device of the present invention, the positive electrode includes a plurality of positive electrode portions and a layered positive electrode layer that form the array structure, and the negative electrode includes a plurality of negative electrode portions that form the array structure and It is preferable that a negative electrode layer is provided, and the positive electrode layer and the negative electrode layer are disposed to face each other with the solid electrolyte body interposed therebetween. In addition, the positive electrode portions and the negative electrode portions constituting the staggered arrangement structure can be arranged in a matrix, and the positive electrode portions and the negative electrode portions constituting the alternate arrangement structure are arranged in parallel bands. May be.

  Moreover, in the all-solid-state electricity storage element of this invention, the said positive electrode and / or the said negative electrode can have a hollow part. Furthermore, a step can be provided between the positive electrode and the negative electrode at the end of the layer.

  Furthermore, the all-solid-state energy storage device of the present invention has a laminated structure in which two or more units are laminated, and the positive electrode portion and the negative electrode portion that form the array structure in the solid electrolyte body are staggered or alternately in the lamination direction. It is also possible to provide the following arrangement structure. Further, two or more units may be stacked such that the positive electrode and / or the negative electrode are arranged symmetrically in the stacking direction via a current collector.

  The all-solid-state energy storage device of the present invention includes a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, and a gel-like solid electrolyte body interposed between and in contact with the positive electrode and the negative electrode. Two or more layers may be provided, and at least one of the layers may have a staggered or alternating arrangement structure of the positive electrode and the negative electrode. According to such an arrangement structure, since the positive electrode and the negative electrode are arranged in a staggered manner or alternately in one layer, the contact area with the solid electrolyte body can be easily increased. In addition, the thickness of the solid electrolyte body between the electrodes can be easily reduced. Furthermore, the thickness of the all-solid power storage element can be suppressed. As a result, an output is improved and an all-solid-state energy storage device with low internal resistance can be obtained. In particular, in a secondary battery, the current value per unit area decreases due to an increase in contact area, and the load on the electrode due to charge / discharge differences is reduced, so that the cycle characteristics are improved. Hereinafter, the positive electrode, the negative electrode, and the electrolyte body will be described, and then the characteristic structure of the all-solid-state energy storage device of the present invention will be described. A method for manufacturing the all-solid-state energy storage device will also be described.

(Positive electrode active material and positive electrode)
As the positive electrode active material, various metal oxides, metal sulfides, and the like can be used. In particular, when a metal oxide is used, secondary battery sintering can be performed in an oxygen atmosphere. Specific examples of such a positive electrode active material include manganese dioxide (MnO ₂ ), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (for example, Li _x Mn ₂ O ₄ or Li _x MnO ₂ ), lithium nickel composite oxide. (Eg, Li _x NiO ₂ ), lithium cobalt composite oxide (Li _x CoO ₂ ), lithium nickel cobalt composite oxide (eg, LiNi _1-y Co _y O ₂ ), lithium manganese cobalt composite oxide (eg, LiMn _y Co) _1-y O ₂ ), spinel-type lithium manganese nickel composite oxide (Li _x Mn _2-y Ni _y O ₄ ), lithium phosphorous oxide having an olivine structure (Li _x FePO ₄ , Li _x Fe _1-y Mn _y PO _4, etc. _Li x CoPO _4), lithium phosphorus oxide having a NASICON structure Things _(such as _{Li x V 2 (PO 4)} 3), include at least one selected from iron sulfate _{(Fe 2 (SO 4) 3} ), vanadium oxide (e.g. _V 2 _{O 5).} In these chemical formulas, x and y are preferably in the range of 0-1.

  In addition to the positive electrode active material, the positive electrode can appropriately include a conductive additive, a binder, a solid electrolyte described later, and the like. Examples of the conductive assistant include acetylene black, carbon black, graphite, various carbon fibers, and carbon nanotubes. Examples of the binder include polyvinylidene fluoride (PVDF), SBR, and polyimide.

(Negative electrode active material and negative electrode)
Examples of the negative electrode active material include carbon, metal compounds, metal oxides, Li metal compounds, Li metal oxides (including lithium-transition metal composite oxides), boron-added carbon, graphite, and compounds having a NASICON structure. Etc. can be used. These may be used alone or in combination of two or more. Examples of the carbon include conventionally known carbon materials such as graphite carbon, hard carbon, and soft carbon. Examples of the metal compound include LiAl, LiZn, Li ₃ Bi, Li ₃ Cd, Li ₃ Sd, Li ₄ Si, Li _4.4 Pb, Li _4.4 Sn, and Li _0.17 C (LiC ₆ ). It is done. The metal _{oxides, SnO, SnO 2, GeO,} GeO 2, In 2 O, In 2 O 3, PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Ag 2 O, AgO, Ag 2 O ₃ , Sb ₂ O ₃ , Sb ₂ O ₄ , Sb ₂ O ₅ , SiO, ZnO, CoO, NiO, FeO and the like. Examples of the Li metal compound include Li ₃ FeN ₂ , Li _2.6 Co _0.4 N, Li _2.6 Cu _0.4 N, and the like. Examples of the Li metal oxide (lithium-transition metal composite oxide) include a lithium-titanium composite oxide represented by Li _x Ti _y O _z such as Li ₄ Ti ₅ O ₁₂ . Examples of the boron-added carbon include boron-added carbon and boron-added graphite. In addition to the positive electrode active material, the negative electrode can appropriately include a conductive additive, a binder, a solid electrolyte described later, and the like. The conductive aid and binder are the same as those already described in the section “Positive electrode active material and positive electrode”. Examples of the compound having a NASICON structure include lithium phosphate compounds (such as Li _x V ₂ (PO ₄ ) ₃ ).

(Gel-like solid electrolyte body)
A polymer gel electrolyte can be used as the gel solid electrolyte body. It is preferable to use an electrolyte containing lithium as a mobile ion.

Preferred electrolytes for use in the polymer gel electrolyte, for example, may be those usually used in a lithium ion battery, for _{example, LiPF 6, LiBF 4, LiClO} 4, LiAsF 6, LiTaF 6, LiAlCl 4, Li 2 It is selected from inorganic acid anion salts such as B ₁₀ Cl ₁₀ and organic acid anion salts such as LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N , Containing at least one lithium salt (electrolyte salt), cyclic carbonates such as propylene carbonate and ethylene carbonate; chain carbonates such as dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate; tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, 1,2-dimethyl Ethers such as xyethane and 1,2-dibutoxyethane; lactones such as γ-butyrolactone; nitriles such as acetonitrile; esters such as methyl propionate; amides such as dimethylformamide; methyl acetate and methyl formate And those using an organic solvent (plasticizer) such as an aprotic solvent in which at least one selected from the group consisting of 2 or more is mixed.

(Current collector)
Conventionally known materials can be used for the positive electrode current collector and the negative electrode current collector. As the current collector material, a conductive metal oxide layer is preferably used. For _{example, SnO 2, In 2 O 3} , ZnO, TiO x (0.5 ≦ x ≦ 2) and the like. These conductive metal oxides may contain a trace element (for example, 10 at% or less) for enhancing conductivity such as Sb, Nb, Ta in the structure. In consideration of high temperature use and life, Cu and Al clad materials are preferable.

(External electrode)
The material constituting the external electrode is not particularly limited. For example, Ag, Ag / Pd alloy, Ni plating, Cu by vapor deposition, and the like can be mentioned. Further, solder plating for mounting may be performed on the surface of the external electrode. The connection form of the external electrode is not particularly limited.

(First embodiment)
1st Embodiment about the all-solid-state electrical storage element of this invention is shown in FIGS. As shown in FIG. 1, 1st Embodiment is related with the all-solid-state electrical storage element 10 which has the arrangement structure where the positive electrode 20 and the negative electrode 40 were arranged in zigzag form. The all-solid-state electricity storage element 10 has a unit 80 that includes a positive electrode 20, a negative electrode 40, and a solid electrolyte body 60. The unit 80 may include at least one electrode-solid electrolyte layer 70 having a positive electrode portion 22 including a positive electrode active material, a negative electrode portion 42 including a negative electrode active material, and a solid electrolyte body 60. The all-solid-state energy storage device 10 includes a positive electrode current collector 30 and a negative electrode current collector 50 on the outside of the positive electrode 20 and the negative electrode 40, respectively. The positive electrode current collector 30 and the negative electrode current collector 50 are connected to appropriate external electrodes (not shown). Hereinafter, the configuration of the all-solid-state energy storage device 10 will be described.

(Configuration of electrode-solid electrolyte layer)
(Solid electrolyte)
As shown in FIG. 1A, the solid electrolyte body 60 is configured to contact the positive electrode 20 and the negative electrode 40. In this embodiment, it is disposed between the positive electrode 20 and the negative electrode 40, fills the space between the positive electrode 20 and the negative electrode 40, and can come into contact with the surface of the positive electrode 20 and the surface of the negative electrode 40. . As described later, the solid electrolyte body 60 can include a positive electrode portion 22 and a negative electrode portion 42. As a result, it can be said that the solid electrolyte body 60 has a lattice-like planar form surrounding the positive electrode portion 22 and the negative electrode portion 42 as shown in FIG. It can also be said that the positive electrode portion 22 and the negative electrode portion 42 are provided inside each lattice of the partitioned solid electrolyte body 60.

(Electrode structure)
In the present embodiment, the positive electrode 20 is arranged in a layered positive electrode layer 24 corresponding to a plane orthogonal to the stacking direction in the all-solid-state energy storage device 10 and dispersed in the positive electrode layer 24 so as to protrude toward the solid electrolyte body 60 side. A plurality of positive electrode portions 22 formed may be provided. The negative electrode 40 includes a layered negative electrode layer 44 corresponding to a plane orthogonal to the stacking direction in the all-solid-state energy storage device 10 and a negative electrode formed in a projecting manner on the solid electrolyte body 60 side by being dispersed in the negative electrode layer 44. A portion 42.

(Positive electrode part)
In the electrode-solid electrolyte layer 70, the positive electrode portions 22 are preferably distributed uniformly. In addition, the shape of each positive electrode portion 22 is not particularly limited, and may be any shape such as a pyramid shape, a cone shape, a truncated cone shape, a truncated pyramid shape, a cube shape, a rectangular parallelepiped shape, a columnar shape, a prism shape, and the like. Can do. Moreover, the convex shape inclined as a whole may be sufficient. In consideration of the moldability and contribution to reducing the thickness of the solid conductive body 60 described later, the shape of the positive electrode 20 is a truncated cone shape, a truncated pyramid shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape, a prismatic shape, or the like. A shape having a top surface is preferred. More preferred are a truncated pyramid shape, a cubic shape, and a rectangular parallelepiped shape. As will be described later, in consideration of the staggered arrangement of the positive electrode portions 22, an isotropic convex body having little anisotropy in at least the plane direction, such as a cubic shape or a prism shown in FIG. 1, can be preferably used. The positive electrode 20 including the positive electrode portion 22 is preferably a substantial solid (including a porous body). In addition, the positive electrode 20 including the positive electrode portion 22 is preferably a substantial solid (including a porous body).

(Negative electrode part)
Similarly to the positive electrode portion 22, the negative electrode portion 42 is preferably uniformly distributed and distributed in the electrode-solid electrolyte layer 70. The shape of each negative electrode portion 42 is not particularly limited, but various shapes as described for the positive electrode portion 22 can be adopted, and a preferable shape for the positive electrode portion 22 is also a preferable aspect in the negative electrode portion 42. it can. In addition, as for the size of the negative electrode portion 42, a preferable size can be adopted in the positive electrode portion 22. Further, the negative electrode 40 including the negative electrode portion 42 is preferably a substantial solid (including a porous body).

(Electrode arrangement structure)
Next, the arrangement structure in the solid electrolyte body 60 by the positive electrode part 22 and the negative electrode part 42 is demonstrated. As shown in FIG. 1B, the all solid state energy storage device 10 of the present embodiment can have an electrode arrangement structure including a positive electrode 20 and a negative electrode 40 in a solid electrolyte body 60. More specifically, an electrode arrangement structure including a positive electrode part 22 that is a part of the positive electrode 20 and a negative electrode part 42 that is a part of the negative electrode 40 can be provided.

  The electrode arrangement structure is preferably an arrangement in which the positive electrode portion 22 and the negative electrode portion 42 are uniformly distributed. As such an array structure, as shown in FIG. 1, a plurality of positive electrode portions 22 are arranged in a zigzag (zigzag) manner in the layer of the solid electrolyte body 60, and a plurality of negative electrode portions 42 are staggered. An array structure having a planar form arranged in a (zigzag) manner is exemplified. Each of the positive electrode portions 22 and the negative electrode portions arranged in a staggered manner is preferably 10 or more, and preferably several tens or more.

  As shown in FIG. 1A, the positive electrode portion 22 and the negative electrode portion 42 are offset so that they do not face each other in the stacking direction of the battery 10 (the center axis is shifted). It is preferable that they are arranged. By not facing each other, it is possible to avoid that the thickness of the solid electrolyte body 60 is locally thinned and easily short-circuited at the facing portion.

  The offset positive electrode portion 22 and negative electrode portion 42 are preferably arranged so that their thicknesses at least partially overlap in the stacking direction. That is, it is preferable that the positive electrode portion 22 and the negative electrode portion 42 have a structure in which they enter the other forming region along the stacking direction. By doing so, the contact area between the positive electrode portion 22 and the negative electrode portion 42 and the solid electrolyte body 60 can be increased without increasing the thickness of the all-solid-state energy storage device 10. Furthermore, the thickness of the solid electrolyte body 60 between the electrodes can be suppressed, and the layer thickness of the electrode-solid electrolyte body layer 70 can also be suppressed, so that the thickness of the all-solid power storage element 10 can also be suppressed.

  Moreover, it becomes possible to comprise a battery in the side surface of the positive electrode part 22 and the negative electrode part 42 by offsetting. That is, the battery 10 can be made to function even in a direction orthogonal to the stacking direction in the layer 70 in which the positive electrode portion 22 and the negative electrode portion 42 are arranged. Furthermore, in the all-solid-state energy storage device 10 of the present embodiment, the positive electrode 20 includes a layered positive electrode layer 24, and the negative electrode 40 includes a layered negative electrode layer 44. For this reason, as shown in FIG. 1, a battery can also be configured between the positive electrode portion 22 and the negative electrode layer 44 and between the negative electrode portion 42 and the positive electrode layer 24. For this reason, the output of the battery 10 can be improved.

  In the solid electrolyte body 60, the positive electrode portion 22 and the negative electrode portion 42 are preferably arranged in a matrix as a whole. That is, it is preferable that the positive electrode portion 22 and the negative electrode portion 42 constitute an m × n matrix. By arranging in a matrix, the contact area between the electrode and the solid electrolyte body 60 can be more effectively increased.

  FIG. 1 is a typical example of an arrangement structure of the positive electrode portion 22 and the negative electrode portion 42. In this arrangement structure, the positive electrode portion 22 and the negative electrode portion 42 are arranged in a matrix as a whole in the layer of the solid electrolyte body 60, and each has an arrangement structure (arrangement structure in plan view). . Further, the positive electrode portions 22 and the negative electrode portions 42 are alternately arranged in the vertical direction and the horizontal direction of the arrangement.

  According to the all-solid-state electricity storage device 10 of the present embodiment described above, since the positive electrode portion 22 and the negative electrode portion 42 have an array structure in which the positive electrode portion 22 and the negative electrode portion 42 are arranged in a zigzag manner, Can be increased. Thereby, the output improvement as the battery 10 can be expected. Moreover, the thickness of the solid electrolyte body 60 between the positive electrode 20 and the negative electrode 40 can be reduced by the arrangement structure in the electrode-solid electrolyte body layer 70. Thereby, internal resistance can be made small. Furthermore, according to the all-solid-state energy storage device 10 of the present embodiment, these effects can be obtained without complicating the structure of the all-solid-state energy storage device 10 due to the arrangement structure of the positive electrode portion 22 and the negative electrode portion 42.

(Stacked all-solid energy storage device)
As shown in FIG. 1, the all-solid-state power storage element 10 may be configured to include only one battery unit 80 (the positive electrode 20, the negative electrode 40, and the solid electrolyte body 60), but the stacked type in which the battery units 80 are stacked. An all-solid energy storage device may be used. An example of a stacked all-solid-state energy storage device is shown in FIG. For example, as illustrated in FIG. 2A, the positive electrode 20 may be laminated so as to be plane-symmetrical via the positive electrode current collector 30 of the all-solid-state energy storage element unit 80, or via the negative electrode current collector 50. You may laminate | stack so that the negative electrode 40 may become plane symmetry. According to such a stacked all-solid-state energy storage device, it is possible to obtain a stacked body that can be easily connected in parallel even with cells adjacent in the stacking direction. Moreover, according to the laminated structure shown to Fig.2 (a), it can collect from the side of the internal electrical power collectors 30 and 50 by providing a electrical power collector in a side surface.

  In addition, the stacked type all solid state power storage element may be formed by stacking the units 80 with an appropriate conductive member interposed therebetween. According to such a stacked type all-solid-state energy storage device, a stacked body in which all-solid-state energy storage devices 10 are connected in series can be obtained.

    Further, as shown in FIG. 2B, the positive electrodes 20 are stacked via the positive electrode current collector 30, and the positive electrode portions 22 of the two positive electrodes 20 sandwiching the positive electrode current collector 30 are staggered in the stacking direction. Can be arranged. According to this arrangement, at the same time, the negative electrode portions 42 of the two negative electrodes 20 arranged to face each positive electrode 20 are also arranged in a staggered manner in the stacking direction. By arranging the positive electrode portion 22 and the negative electrode portion 42 in a staggered manner in the stacking direction, internal stress during charging and discharging can be relaxed. Moreover, according to this lamination | stacking form, the positive electrode part 22 and the negative electrode part 42 are alternately arrange | positioned in the lamination direction. In the configuration shown in FIG. 2B, the positive electrode 20 is disposed so as to sandwich the positive electrode current collector 30, but the negative electrode 40 may be disposed so as to sandwich the negative electrode current collector 50. However, both of these configurations may be provided.

  As described above, according to the laminated all solid state storage element in which the all solid state storage element 10 having the staggered electrode arrangement structure is stacked, the degree of freedom of electrical connection between cells formed in the battery 10 is improved. However, it is possible to easily meet the demand for output and the like by adopting a connection form as necessary.

(Manufacturing method of all-solid-state energy storage device)
Next, an example of a method for manufacturing the all-solid-state energy storage device 10 of the present embodiment will be described with reference to FIGS.

(Preparation process of solid electrolyte body)
First, the solid electrolyte body 100 is prepared. The solid electrolyte body 100 supplies a positive electrode active material and a negative electrode active material to form at least a part of the positive electrode 20 and the negative electrode 40 (specifically, the positive electrode part 22 and the negative electrode part 42), a recess 102a, 102b. Such a solid electrolyte body 100 can also be produced by molding a solid electrolyte material or physically or chemically processing a precursor having a predetermined shape.

  The solid electrolyte body 100 having the recesses 102a and 102b can be produced, for example, as shown in FIG. That is, three types of solid electrolyte sheets (unfired ceramic green sheets and the like) 110, 120, and 130 are prepared. The first solid electrolyte sheet 110 can have holes (cells) 112 in an m × n matrix. The hole portion 112 is a portion where the positive electrode portion 22 and the negative electrode portion 42 are finally formed, respectively.

  The second solid electrolyte sheet 120 has a hole 122 corresponding to the position and size of the positive electrode 20 of the all-solid energy storage device 10. The third solid electrolyte sheet 130 has a hole 132 corresponding to the position and size of the negative electrode 40 of the all-solid-state energy storage device 10. By laminating these three types of solid electrolyte sheets 110, 120, and 130, one surface has a recess 102 a that opens corresponding to the positive electrode portion 22, and the other surface corresponds to the negative electrode portion 42. Thus, it is possible to obtain the solid electrolyte body 100 having the recessed portion 102b that opens.

  The solid electrolyte body 100 and the individual solid electrolyte sheets 110, 120, and 130 are made of a constituent material of the solid electrolyte body such as a binder (for example, polyvinylidene fluoride, styrene butadiene rubber) and a solvent (N-methylpyrrolidone, water, etc.). After the slurry kneaded in (1) is applied to a carrier sheet to a thickness required by screen printing or a doctor blade method, it can be formed by removing the carrier sheet. The timing of firing is appropriately determined depending on the matching between the solid electrolyte and the positive electrode / negative electrode active material, specifically, the relationship between the firing temperature and the firing shrinkage rate. As an example, the solid electrolyte sheets 110, 120, and 130 may be stacked and then fired, and then the positive electrode and the negative electrode may be formed. According to this, since it is not necessary to prepare the firing temperature in the combination of the solid electrolyte and the positive electrode / negative electrode active material, the options for the combination are widened, and when the positive electrode / negative electrode active material is filled, the positive electrode / negative electrode active material is expanded. The solvent or the like contained in the slurry can prevent the pressure-bonded portion of the solid electrolyte from peeling off.

(Formation process of positive electrode and negative electrode)
Next, a positive electrode active material and a negative electrode active material are supplied to the recesses 102a and 102b of the solid electrolyte body 100 in a staggered manner or alternately. These active materials are supplied in the form of a slurry or the like, and can be used by appropriately selecting dipping, discharging, injection, various printing methods, and the like. FIG. 4 shows a state in which the positive electrode active material and the negative electrode active material are supplied and filled in the recesses 102a and 102b of the solid electrolyte body 100, respectively.

  Further, the positive electrode layer 140 and the negative electrode layer 150 are formed on the solid electrolyte body 100. As shown in FIG. 5, a positive electrode layer 140 is formed by laminating a green sheet of a positive electrode active material or printing a positive electrode active material on the surface of the solid electrolyte body 100 where the recess 102 a is opened. Further, the negative electrode layer 150 is formed on the surface of the solid electrolyte body 100 where the hole 102b is opened by laminating a green sheet of a negative electrode active material or printing the negative electrode active material. Note that the positive electrode layer 140 or the negative electrode layer 150 can be simultaneously formed by printing or the like simultaneously with the step of supplying the active material to the holes 102a and 102b. Thereby, the battery unit 80 can be obtained.

(Current collector formation process)
Further, as shown in FIG. 6, the positive electrode current collector layer 170 and the negative electrode current collector layer 180 are formed by laminating or printing a current collector sheet on each of the positive electrode layer 140 and the negative electrode layer 150. To do. Thereby, the battery 10 can be obtained.

  In the manufacturing process described above, when each material that can be fired is used, after forming the solid electrolyte body 100, or after forming the positive electrode and / or the negative electrode, and after forming the current collector layers 170 and 180, It may be fired at each step. In particular, in the case of a material that can be cofired, two or more types of material layers may be fired simultaneously, or finally fired after the current collector layers 170 and 180 are formed. May be. In addition, lamination | stacking of each layer can also be performed by thermocompression bonding suitably. Firing conditions can be appropriately set according to the type of material to be fired.

  Further, by stacking the battery units 80 thus obtained, various types of stacked all solid state power storage elements shown in FIG. 2 and the like can be obtained.

  In order to finally obtain an all-solid-state energy storage device that can be charged and discharged, the metal terminals of the external electrodes connected to the positive electrode current collector 170 and the negative electrode current collector 180 are respectively bonded with a conductive paste and dried. It is sufficient to coat and harden the exterior by resin coating by dipping or the like.

  According to the method for manufacturing an all-solid-state energy storage device described above, a solid electrolyte body 100 having a recess capable of supplying at least a part of the positive electrode 20 and the negative electrode 40 by supplying a positive electrode active material and a negative electrode active material is prepared in advance. Thus, it is possible to easily obtain an arrangement structure in which the positive electrode 20 and the negative electrode 40 are staggered or alternately arranged. In particular, since the active material supply sites are formed in the recesses 102a and 102b, the active material can be easily supplied and filled. In addition, according to this manufacturing method, the convex positive electrode portion and the negative electrode portion can be easily and accurately formed simply by supplying the active material to the recesses 102a and 102b formed in advance. As a result, even an electrode group having a staggered or alternating arrangement structure can be easily manufactured.

  In this embodiment, the solid electrolyte body 100 having the recesses 102a and 102b is prepared in advance, and the recesses 102a and 102b are filled with the active material to obtain a staggered or alternating electrode arrangement structure. It is not limited to. For example, as shown in FIG. 7, the active material is added so that a predetermined arrangement structure is obtained in the holes 112, 122, 132 of the first to third solid electrolyte sheets 110, 120, 130 shown in FIG. After supplying and filling, these solid electrolyte sheet 110, 120, 130 may be laminated and integrated.

(Second Embodiment)
The second embodiment is a modification of the first embodiment. Hereinafter, the same members as those in the first embodiment will be described using the same reference numerals. The all-solid-state energy storage device 210 of the present embodiment has an electrode arrangement structure in which at least a part of the positive electrode 220 and at least a part of the negative electrode 240 are not staggered but simply alternate. An example of such an electrode arrangement structure is shown in FIG. In the arrangement structure illustrated in FIG. 8, the band-like positive electrode portions 222 and the negative electrode portions 242 are alternately arranged in the solid electrolyte body 60 so as to be parallel to each other. In this way, in all solid state power storage element 210, a battery can be configured in a direction orthogonal to the stacking direction. Further, similarly to the first embodiment, the positive electrode layer 224 and the negative electrode layer 244 may be provided so as to be integrated with the alternately arranged structure portion of the positive electrode portion 222 and the negative electrode portion 242 and arranged in an opposing manner. In this case, a battery can be formed between the positive electrode layer 222 and the negative electrode layer 242.

  When the positive electrode portions 222 and the negative electrode portions 242 are alternately arranged in the solid electrolyte body 60, one end of the band-shaped positive electrode portion 222 is connected to the solid electrolyte body 60 as shown in FIG. One side a is exposed and the other end is sealed with the solid electrolyte body 60, and one end of the band-shaped negative electrode portion 242 is exposed on the side b opposite to the one side of the solid electrolyte body 60. It is preferable to seal the end of the solid electrolyte body 60. In this way, as shown in FIG. 9 (a), the positive electrode current collector 30 is arranged on one side surface a, and the negative electrode current collector 50 is arranged on the other side surface b, thereby collecting from the side. Electricity is possible. In the case of such an array structure, the positive electrode layer 224 and the negative electrode layer 244 can be omitted (see the intermediate layer in FIG. 9B).

  In addition, as shown in FIG. 9B, when a stacked type all-solid-state energy storage device is configured, current is collected on the side surface by stacking positive electrode portions 222 and negative electrode portions 242 alternately in the stacking direction. Since the internal current collector, the uppermost current collector and the electrode can be omitted by arranging the body, a compact laminated structure can be obtained. Furthermore, in the form shown in FIG. 9B, the positive electrode portion 242 and the negative electrode portion 244 are arranged in a staggered manner in the stacking direction, and as a result, the internal stress during charge / discharge can be relieved. it can.

    In addition, about the aspects of the positive electrode 220 and the negative electrode 240 and the positive electrode part 242 and the negative electrode part 244 in this embodiment, the various aspects described in the first embodiment can be applied to aspects other than the electrode arrangement structure described above.

  Next, an example of the manufacturing method of the all-solid-state energy storage device of this embodiment will be described with reference to an example of manufacturing the stacked-type all-solid energy storage device shown in FIG.

(Preparation process of solid electrolyte body)
First, the solid electrolyte body 300 is prepared. In the present embodiment, as shown in FIG. 10, a solid electrolyte body 300 having recesses 302 a and 302 b that open to the side surfaces facing each other so as to be able to supply the band-shaped positive electrode portion 222 and the negative electrode portion 242 is prepared. Similar to the first embodiment, such a solid electrolyte body 300 can be obtained by stacking, cutting, drilling, or the like of a solid electrolyte sheet or screen printing.

(Formation process of positive electrode and negative electrode)
Next, the positive electrode portion 222 and the negative electrode portion 242 are alternately arranged in the hole 302 of the solid electrolyte body 300 so that the positive electrode portion 222 and the negative electrode portion 242 are alternately arranged in the stacking direction. The active material can be supplied and filled so that FIG. 11 shows a state in which the positive electrode active material or the negative electrode active material is supplied and filled in the recesses 302a and 302b of the solid electrolyte body 300, respectively.

(Current collector formation process)
Further, as shown in FIG. 12, a predetermined active material layer is formed on the upper and lower surfaces of the solid electrolyte body 300, a predetermined current collector layer is formed, and the positive electrode portion 222 and the negative electrode portion 242 are respectively exposed. A current collector layer is also formed on the side surface. In order to finally obtain an all-solid-state power storage device that can be charged and discharged, as in the first embodiment, the metal terminals of the external electrodes connected to the current collector are bonded to each other with a conductive paste and dried. After that, the exterior by resin coating may be coated and hardened by dipping or the like.

  In addition, the manufacturing method of the all-solid-state electricity storage element of this embodiment is not limited to the above-described manufacturing example, and it is possible to appropriately change the processing in each process, the processing order in the process, the order of the processes, and the like. . For example, when the solid electrolyte and the positive electrode / active material can be co-fired, firing may be performed after all layers are stacked by a screen printing method or a sheet lamination method.

(Third embodiment)
The all-solid-state power storage element 310 of the present embodiment can have a hollow portion in at least a part of the positive electrode 320 and / or the negative electrode 340 that form an array structure in the solid electrolyte body 60. FIG. 13 shows an example of such an electrode structure. In the following description, members common to the first embodiment will be described using the same reference numerals. The electrode arrangement structure in the present embodiment is a part of the positive electrode 320 disposed in the solid electrolyte body 60 and is a part of the positive electrode portion 322 and the negative electrode 340 protruding to the solid electrolyte body 60 side. It is comprised from the negative electrode part 342 protruded to the body 60 side.

    In the present embodiment, hollow portions 330 and 350 can be provided inside the positive electrode portion 322 and the negative electrode portion 342, respectively. The hollow portions 330 and 350 of the positive electrode portion 322 and the negative electrode portion 342 that are arranged may communicate with other adjacent layers such as the solid electrolyte body 60 and the current collectors 30 and 50, or the electrode 320. 340 may be a closed space within 340. When the hollow portions 330 and 350 communicate with other layers, the electrodes 320 and 340 may take a cylindrical shape or a container shape having a bottom portion. Moreover, when the electrode active material which comprises such electrodes 320 and 340 is thin, it may be said that it is a skin-like body rather than having the hollow parts 330 and 350. Since the all-solid-state energy storage device 310 has the hollow or skin-shaped electrodes 320 and 340 in the arrangement structure as described above, the output per unit weight of the all-solid-state energy storage device 310 can be improved. In addition, also when making the positive electrode 320 and the negative electrode 340 hollow or outer-shell shape, the various aspects of the electrode demonstrated in 1st Embodiment and 2nd Embodiment are applicable. For example, as the external shape or contour shape of the electrode, any of the electrode shapes described in the first embodiment can be adopted, and the band-like aspect described in the second embodiment can also be adopted. . Regarding the arrangement structure of the electrodes, any of the aspects described in the first embodiment can be employed, and the aspect described in the second embodiment can also be employed. Furthermore, the lamination | stacking form demonstrated by each embodiment can also be taken.

  The all-solid-state electricity storage element 310 of this embodiment can be manufactured according to the manufacturing method of the all-solid-state electricity storage element of 1st Embodiment. That is, in the step of forming the positive electrode and the negative electrode described above, instead of supplying and filling the active material into the recess 102 of the solid electrolyte body 100, the active material is formed on the inner wall of the recess 102 so that the hollow portion remains inside the recess 102. What is necessary is just to apply | coat a substance and to supply.

  The present invention is not limited to the above-described embodiment, and can be carried out within the scope of the present invention. For example, in the embodiment described above, an example of a planar secondary battery in which a flat layered electrode and an electrolyte are stacked with respect to the shape of the all-solid-state power storage element has been described, but the battery shape is not limited thereto. For example, a cylindrical shape, a rod shape, or the like may be used.

  Further, the staggered or alternating arrangement structure which is a feature of the present invention can be applied not only to the all-solid-state power storage element but also to other uses. As an application example, a capacitor can be mentioned by using lithium metal or carbon material for the positive electrode / negative electrode. Here, in a form having a hollow shape or a skin shape as in the third embodiment, a liquid electrolyte can be used. Moreover, in 3rd Embodiment, it is applicable also as a reactor, for example, it can apply as a fuel cell.

The figure which shows an example of the all-solid-state electrical storage element of 1st Embodiment. The figure which shows an example of the laminated | stacked all-solid-state electrical storage element of 1st Embodiment. The figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 1st Embodiment. The figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 1st Embodiment. The figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 1st Embodiment. The figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 1st Embodiment. The figure explaining the other example of manufacture of the all-solid-state electrical storage element of 1st Embodiment. The figure which shows an example of the all-solid-state electrical storage element of 2nd Embodiment. The figure (a) which shows the arrangement structure of the all-solid-state electrical storage element of 2nd Embodiment, and the figure (b) which shows an example of a laminated | stacked all-solid-state electrical storage element. The figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 2nd Embodiment. It is a figure which shows a part of manufacturing process of the all-solid-state electrical storage element in 2nd Embodiment, (a) is the figure seen from the side surface in which the positive electrode part 222 is exposed, (b) is the negative electrode part 242 It is the figure seen from the side surface exposed. The figure which shows a part of manufacturing process of an all-solid-state electrical storage element in 2nd Embodiment. The figure which shows an example of the all-solid-state electrical storage element of 3rd Embodiment.

Explanation of symbols

10, 210, 310 All-solid-state power storage element, 20, 220, 320 Positive electrode, 22, 222, 322 Positive electrode portion, 24, 224 Positive electrode layer, 40, 240, 340 Negative electrode, 42, 242, 342 Negative electrode portion, 44, 244 Negative electrode Layer, 30 positive electrode current collector, 50 negative electrode current collector, 60, 100, 300 solid electrolyte body, 70 electrode-solid electrolyte body layer, 80 units, 102a, 102b recess, 110, 120, 130 solid electrolyte sheet, 112, 122, 132 hole part, 140 positive electrode layer, 150 negative electrode layer, 170 positive electrode current collector layer, 180 negative electrode current collector layer, 330, 350 hollow part.

Claims (8)

A positive electrode having a positive electrode active material;
A negative electrode having a negative electrode active material;
A gel-like solid electrolyte body in contact with the positive electrode and the negative electrode;
Comprising one or more units having
The all-solid-state electricity storage element which has a staggered or alternating arrangement | sequence structure by the at least one part of the said positive electrode and the at least one part of the said negative electrode in the solid electrolyte body in at least one said unit. The positive electrode includes a plurality of positive electrode portions and a layered positive electrode layer forming the array structure,
The negative electrode includes a plurality of negative electrode portions and a layered negative electrode layer forming the array structure,
The all-solid-state energy storage device according to claim 1, wherein the positive electrode layer and the negative electrode layer are disposed to face each other with the solid electrolyte body interposed therebetween.   The all-solid-state energy storage device according to claim 1, wherein the positive electrode portion and the negative electrode portion constituting the staggered arrangement structure are arranged in a matrix.   3. The all-solid-state energy storage device according to claim 1, wherein the positive electrode portions and the negative electrode portions constituting the alternating arrangement structure are arranged in a band shape parallel to each other.   The all-solid-state energy storage device according to claim 1, wherein the positive electrode and / or the negative electrode has a hollow portion.   The all-solid-state electrical storage element in any one of Claims 1-5 provided with a level | step difference between the said positive electrode and the said negative electrode in the edge part of the said layer. The all-solid-state energy storage device includes a laminated structure in which two or more units are laminated,
7. The all-solid-state energy storage device according to claim 1, wherein the positive electrode portion and the negative electrode portion that form an array structure in the solid electrolyte body have a staggered or alternating array structure in the stacking direction.   The all-solid-state energy storage device according to claim 7, wherein two or more of the layers are stacked such that the positive electrode and / or the negative electrode are arranged in plane symmetry in the stacking direction via the current collector.