JPH067496B2 - Solid electrochemical device - Google Patents

Abstract

PURPOSE:To make a device thin and to increase its area by filling a mixture prepared by dispersing solid electrolyte powder and/or electrode material powder in a polymer elastomer in the openings of a net to form a sheet, and using the sheet as a solid electrolyte layer and/or an electrode layer. CONSTITUTION:A solid electrochemical device is obtained by stacking a pair of electrode layers on both sides of a solid electrolyte layer, then uniting them. The solid electrolyte layer and/or the electrode layer are/is obtained by filling a mixture prepared by dispersing solid electrolyte powder and/or electrode material powder in a polymer elastomer in the openings of a net to form a sheet. The volume fraction of the solid electrolyte powder to the polymer elasto mer in the solid electrolyte layer is limited to 55-95%. The volume fraction of the electrode material powder and the solid electrolyte powder which is mixed if necessary to the polymer elastomer in the electrode layer is limited to 75-95%, or the volume fraction of the solid electrolyte to the polymer elasto mer is limited to 55-95%.

Description

TECHNICAL FIELD The present invention relates to a solid-state electrochemical device, and more particularly to a solid-state electrochemical device used in a solid-state battery, a solid-state electric double layer capacitor, a solid-state electrochromic display, or the like. .

[Conventional technology]

The solid-state electrochemical device has the advantages that since all the material components are solid substances, there is no liquid leakage, and it is easy to make the device compact and thin. When constructing such an element,
A solid state ionic conductor for moving ions inside the device, that is, a solid electrolyte is required. The solid electrolyte is distinguished by a mobile ion species, and includes Li ⁺ ion conductive solid electrolyte, Ag ⁺ ion conductive solid electrolyte, Cu ⁺ ion conductive solid electrolyte, H ⁺ ion conductive solid electrolyte, and the like. A solid electrochemical element is constructed by combining the solid electrolyte and an electrode material, and usually, a pair of electrode layers are arranged on the upper and lower surfaces of the solid electrolyte powder layered by pressure pressing.

In an electrochemical device using a liquid electrolyte, electrical and ionic bonding between the electrolyte and the electrode material is easy, whereas in a solid electrochemical device using a solid substance, solid electrolytes, electrode materials or solid electrolytes and electrodes are used. Electrical and ionic bonding with materials is generally difficult. In an element using a liquid electrolyte, in order to prevent the electrolyte from flowing out or to prevent the electrolyte from penetrating into the electrode too much and causing the shape of the electrode to collapse, the electrolyte or the electrode is mixed with a contaminant such as an adhesive. . However, in the solid-state electrochemical device, if contaminants are mixed in, electrical and ionic bonding becomes more difficult, and thus the contaminants cannot be used. Therefore, when producing a solid electrochemical element using a solid electrolyte or electrode material that is an inorganic solid powder, it is necessary to pelletize by a high pressure press, and since the resulting pellets are hard and brittle, productivity and uniform It is a major obstacle to getting sex. That is, in joining the electrode material and the solid electrolyte, it is necessary to bring them into close contact with each other with a large pressure, but in the case of a large area solid electrochemical element, it is difficult to obtain uniform adhesion, and if too much pressure is applied, the solid This causes problems such as damage to the electrode layer and internal short circuit.

[Problems to be solved by the invention]

An object of the present invention is to solve the above-mentioned problems of the prior art, to achieve thinning and a large area, easy handling of element constituent materials, workability in assembling elements, productivity, etc. Another object of the present invention is to provide an excellent solid-state electrochemical device.

[Means for solving problems]

A sheet-like molded product having a solid electrolyte layer and at least a pair of electrode layers joined to the upper and lower surfaces through the solid electrolyte layer, wherein at least one of the solid electrolyte layer and the electrode layer uses a reticulate body as a carrier. Wherein the solid electrolyte layer contains a mixture of solid electrolyte powder dispersed in a polymer elastic body, and at least one of the electrode layers comprises:
It contains a solid electrolyte powder or a mixture of a solid electrolyte powder and a powder of electric charge material dispersed in a polymer elastic body, and the polymer elastic body is a styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block. At least one of a copolymer, a styrene-ethylene-butylene-styrene block copolymer and a 1,2-polybutadiene
At least one of the solid electrolyte layer and the electrode layer is made of a seed, and the mixture is filled in the opening of the mesh body.

The solid electrochemical element in the present invention is basically obtained by integrally molding a solid electrolyte layer and at least a pair of electrode layers on the upper and lower surfaces of the solid electrolyte layer. The method of integrally molding is not particularly limited, but, for example, 100% under an inert gas.
A method of heating and pressurizing at a temperature of about 150 ° C for about several tens of seconds to 10 minutes can be mentioned. After heating and pressurizing, heat treatment may be performed for about 1 to 3 hours in order to make the adhesion force uniform under an inert gas. In addition, if necessary, after placing the extraction electrode (current collector) on the integrally molded body, a simple sealing technique,
For example, it is put into practical use by resin sealing with an epoxy resin or the like or laminate sealing with a polyethylene film, a polypropylene film or the like.

The solid-state electrochemical device thus obtained is easy to manufacture, has flexibility, is thin, and has a large area.

The solid electrolyte powder used in the present invention includes LiI, L
_{iO · H 2 O, Li 3} N · Li 4 SiO 4 -Li 3 PO
Li ⁺ ion conductive solid electrolyte such as _4, RbAg
₄ I ₅ , KAg ₄ I ₅ , Ag ₃ SI, AgI-Ag ₂ O
-Ag ⁺ ion conductive solid electrolyte such as MoO ₃ glass,
RbCu ₄ I _2−x Cl _{3 + x (x = 0.2 to 0.6)} ,
_CuJ-Cu Cu ⁺ ion conductive solid electrolyte such as 2 O-MoO _{3 glass, H 3 Mo 12 PO 40 ·} 29H 2 O, H 3
W ₁₂ PO ₄₀ · 29H ₂ O or the like ^{H +} ion conductive solid electrolyte, sodium beta - alumina _(Na-β-Al 2 O
₃ ), Na ⁺ ion conductive solid electrolytes represented by Na _{1 + a} Zr ₂ P _2-a Si _a O ₁₂ (a = 0 to 3), and the like.

Of these solid electrolytes, RbCu ₄ I _1.75 C
l _3.25 , RbCu ₄ I _1.5 Cl _3.5 , RbCu ₄ I _1.25 C
R _3.75 etc. RbCu ₄ I _2−x Cl _{3 + x} (x = 0.
The Cu ⁺ ion conductive solid electrolyte represented by 6) has a high ion conductivity of 10 ⁻² s / cm at room temperature and is particularly preferable.

Examples of the electrode material powder used in the present invention include graphite, acetylene black, carbon materials such as activated carbon, titanium sulfide, niobium sulfide, molybdenum sulfide, copper sulfide, silver sulfide, lead sulfide, silver shubrel, copper shubrel, iron sulfide and the like. Oxides such as sulfide, tungsten oxide, vanadium oxide, chromium oxide, molybdenum oxide, titanium oxide, iron oxide, silver oxide and copper oxide, halides such as silver chloride, lead iodide and copper iodide, copper,
Examples thereof include silver, lithium, gold, platinum, titanium, alloys of these metals, and metallic materials such as stainless steel.

Further, when the electrode material powder and the solid electrolyte powder are present in the electrode layer, the ratio of the electrode material powder / the solid electrolyte powder is 1/4 to
5/4 (weight ratio) is preferable.

The polymer elastic material used in the present invention includes a styrene-butadiene-styrene block copolymer, styrene-isoprene-, in terms of adhesiveness with the electrode material powder and the solid electrolyte powder.
At least one of a styrene block copolymer, a styrene-ethylene-butylene-stalene block copolymer and 1,2-polybutadiene is used. Among these, those having an ASTM-A hardness of 90 or less are preferable from the viewpoint of flexibility. Also, from the viewpoint of the heat resistance of the solid electrolyte powder, 150
Those having moldability at a temperature of not higher than 0 ° C are preferable.

As the solid electrolyte layer in the present invention, a solid electrolyte powder is uniformly dispersed in a polymer elastic body at a volume fraction of preferably 55 to 95%, more preferably 75 to 92%. It is preferable to use an electrolyte sheet which is filled in the openings.

When the volume fraction of the solid electrolyte powder is less than 55%, the ionic conductivity is 1/1000 to 1 / 10,000 compared with the powder state.
To 1 × 10 ⁻⁶ s / cm or less even in the RbCu ₄ I _2−x Cl _{3 + x} system, which has the highest conductivity, and has a volume fraction of 95.
If it exceeds%, the solid electrolyte sheet obtained when formed into a sheet may be brittle and may easily fall off.

As the electrode layer in the present invention, the electrode material powder and the solid electrolyte powder are preferably contained in the elastic polymer in a volume fraction of 75-
The electrode layer obtained by filling the openings of the mesh body with the mixture dispersed so as to be 95%, or the solid electrolyte powder is dispersed in the polymer elastic body, preferably so as to have a volume fraction of 55 to 95%. It is preferable that the electrode layer is formed by filling the mixture with the mixture in the opening of the conductive mesh body that also serves as an electrode material. If the volume fraction is less than 75%, the contact efficiency between the electrode material powder in the electrode layer and the solid electrolyte powder is reduced, and sufficient polarization characteristics cannot be obtained as an electrode. If the volume fraction exceeds 95%, When it is formed into a sheet, it may become brittle and easily fall off.

Further, the electrode layer in the present invention, a plurality of sheets obtained by gradually changing the mixing ratio of the electrode material powder and the solid electrolyte powder are laminated in the order of the mixing ratio, and the solid electrolyte powder has a large mixing ratio of the electrode layer surface. It is preferred to be joined with the layer.

The shape and particle size of the solid electrolyte powder and the electrode material powder used in the present invention are not particularly limited, but from the viewpoint of ease of mixing with the elastic polymer, 100-200 mesh (Tyler standard) Those that pass through a sieve are preferred.

The method for obtaining a solid electrolyte layer mixture or an electrode layer mixture by uniformly dispersing the solid electrolyte powder or the solid electrolyte powder and the electrode material powder in the polymer elastic body is not particularly limited, but for example, a polymer Examples thereof include a method of kneading a polymer solution in which an elastic body is dissolved in a specific solvent, solid electrolyte powder, electrode material powder and the like with a ball mill or the like. This method
The heat generated during kneading is low, and the solid electrolyte powder, electrode material powder, etc. are unlikely to deteriorate or decompose, and there is almost no contact with the atmosphere during kneading, so it is difficult for the powder to change or decompose due to oxygen, etc. It is preferable as a manufacturing method because it is not necessary to control the temperature, oxygen and other conditions.

The solvent used in this case is, for example, n-hexane, n-heptane, n-octane, cyclohexane, benzene, toluene, xylene, ethyl acetate, trichlene, etc. It is preferable to use a hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent or an ester solvent.

Examples of the material of the mesh body used in the present invention include cellulose, nylon 6, nylon 66, polypropylene,
Non-conductive materials such as polyethylene, silica, alumina, glass, conductive carbon such as activated carbon, copper, nickel,
Conductive materials such as titanium and stainless steel can be used, and specific examples of the mesh body include woven and non-woven fabrics made of these materials. The aperture ratio of these mesh bodies is appropriately in the range of 35 to 65%. The opening ratio is defined as the ratio of the total opening area per unit area of the mesh body.
If the solid electrolyte layer has an aperture ratio of less than 35%,
The electrical conductivity becomes small, the polarization becomes large when it is used as an electrode layer, and if the aperture ratio exceeds 65%, the effect of maintaining the strength as a layer cannot be obtained, which is not preferable. Further, the specific surface area of these reticulate bodies is suitably in the range of 50 to 1000 m ² / g. Further, in the case of a non-woven fabric, a basis weight of 5 to 50 g / m ² is suitable. The thickness of the reticulated body is 10 to 150 μm in the case of the non-conductive reticulated body and 30 to 300 μm in the case of the conductive reticulated body in consideration of the strength of the reticulated body itself and the thinning of the element.
The range of m is preferable, and the average area per opening is 1.
6 × 10 ^{−3 to} 9 × 10 ⁻² mm ² and the width between adjacent openings are preferably 20 to 120 μm.

As a method of filling the mixture of the solid electrolyte layer or the mixture for the electrode layer into the openings of the reticulated body, for example, the reticulated body is immersed in a slurry in which the mixture is dispersed in a solvent, and the mixture is sufficiently mixed in the reticulated body. After the adhesion, a method of filling the opening with a blade made of hard rubber, plastic, metal or the like, a roll or the like and removing the excessively adhered mixture may be mentioned. The solid content concentration of the mixture in the slurry at this time is preferably 50 to 80% by weight.

After filling the mixture in the openings of the reticulate body in this way,
For example, by drying at 20 to 30 ° C., preferably in an inert gas atmosphere, the solid electrolyte layer and electrode layer used in the solid electrochemical device of the present invention can be obtained. Incidentally, these layers, solid electrolyte powder, electrode material powder, in the opening of the mesh body,
It is composed of a mixture of polymer elastic material,
In order to improve the adhesion to the electrode layer, the solid electrolyte layer, or the extraction electrode, and the conductivity, polarizability, capacity, etc., the mixture layer having 5 to 25 μm on each of the upper and lower sides or one side of the mesh body is required. Is preferred.

According to the above method, it is possible to obtain a solid electrolyte layer or an electrode layer having extremely excellent thickness accuracy because the reticulate body is used as a base material, and since these can be continuously manufactured, a large area layer can be easily formed. Can be obtained. Therefore, a solid electrochemical device having a large area, a thin shape, and a uniform thickness can be easily obtained.

The thickness of the solid electrolyte layer and the electrode layer is from 10 to 10, respectively.
˜250 μm is preferable.

In order to increase the adhesive strength with the respective layers, the solid electrolyte layer and the electrode layer of the present eight include, for example, modified rosin, rosin derivative, terpene resin, coumarone-indene resin, phenol-modified coumarone-indene resin, etc. in the mixture. It may contain a rosin-based tackifier, an aromatic-based tackifier or a terpene-based tackifier.

The solid electrolyte powder or the polymer elastic body contained in the solid electrolyte layer and the electrode layer may be the same or different, but from the aspect of the homogeneity of the molded body, the adhesiveness between the solid electrolyte layer and the electrode layer, and the like. It is preferable to use the same one.

The material of the extraction electrode used in the present invention is not particularly limited, but from the viewpoint of adhesiveness with the electrode layer, a copper thin plate in the case of a copper-based electrode layer, a silver-based electrode layer in the case of a silver-based electrode layer. A silver thin plate is preferable, but a copper thin plate plated with nickel or gold, or an alloy such as phosphor bronze may be used.

In the present invention, the electrode layer gradually changes the mixing ratio of the solid electrolyte powder and the electrode material powder from the surface in contact with the solid electrolyte layer, the ratio of the solid electrolyte powder in the surface in contact with the solid electrolyte layer is large, and the extraction electrode It is preferable that a plurality of sheets are laminated in the order of the mixing ratio to form a multilayered electrode layer so that the ratio of the solid electrolyte powder becomes smaller as it gets closer. The degree of multi-layering of the electrode layer in this case is not particularly limited, and two layers are effective, but preferably 3 to 9 layers. However, in order to avoid the complexity of processing and thickening,
Six layers are suitable. By thus forming the multi-layered electrode layer, the effect of reducing the interface resistance between the electrode and the electrolyte and increasing the current capacity can be obtained.

In the present invention, a solid secondary battery can be obtained by combining the solid electrolyte with an electrode material that electrochemically gives and receives ions to and from the solid electrolyte, such as titanium disulfide and copper shubrel. A solid electrochemical display element (electrochromic display) can be obtained by using a solid electrolyte and an electrode material that electrochemically exchanges ions with the solid electrolyte to cause an optical change, for example, tungsten oxide. . Further, a solid electric double capacitor can be formed by using an electrode material which does not exchange ions between the solid electrolyte and the solid electrolyte but forms an electric double layer at the interface with the solid electrolyte, such as activated carbon. .

According to the present invention, such a solid-state electrochemical device is also excellent in flexibility and extremely strong against mechanical impact.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1 CuCl, CuI and RbCl in molar ratio CuCl:
Each was weighed so that the ratio was CuI: RbCl = 2.5: 1.5: 1.

The CuCl and Cul were recrystallized in hydrochloric acid, and these were vacuum dried in a desiccator containing a P ₂ O ₅ desiccant, while the RbCl was vacuum dried at 100 ° C. and a predetermined amount of these component salts were mixed, After heating at 130 ° C for 17 hours to completely dehydrate, this was vacuum-enclosed in a Pyrex glass tube, thawed and then cooled to room temperature, and the solidified substance was well pulverized with a ball mill using toluene as a dispersant, and pulverized. The resulting powder was pressure-molded, and this was molded in N ₂ at 130 ° C. for 17 hours.
After being treated for about an hour, the obtained pressure-molded product was pulverized again with a ball mill to obtain RbCu ₄ I _1.5 Cl _3.5 powder.

Next, 1 part (part by weight, the same applies hereinafter) of styrene-butadiene-styrene rubber block copolymer (specific gravity: 0.96, manufactured by Nippon Synthetic Rubber Co., Ltd.) as a polymer elastic material was dissolved in toluene to give a high polymer. A molecular solution is obtained, to which 4.22
RbCu ₄ I _1.5 Cl _{3.5 with} a particle size of 200 mesh or less
Was added and kneaded for 2 hours in a ball mill, and the resulting mixture was transferred to a polyethylene container to prepare a solid content concentration of 79% by weight. On the other hand, as a woven fabric, the thickness is 50 μm, the average area per opening is 5.5 × 10 ⁻³ mm ^2, and the width between adjacent openings is 5
Using a 0 μm nylon woven fabric, this woven fabric is dipped in a mixture in a polyethylene container to allow the mixture to adhere sufficiently to the surface of the woven fabric, and then the woven fabric is sandwiched with a blade made of fluororubber, While applying a clamping force, the woven fabric was pulled out from the blade, and the mixture was filled in the opening of the woven fabric. The obtained sheet was sufficiently dried in a nitrogen stream to remove toluene to obtain a solid electrolyte sheet having a volume fraction of solid electrolyte powder in the mixture of 90% and a thickness of 70 μm.

Next, Cu powder, Cu ₂ S powder and RbCu ₄ I
Solid electrolyte powder consisting of _1.5 Cu _3.5 in a weight ratio of Cu: Cu
₂ S: RbCu ₄ I _1.5 Cl _3.5 = 2.9: 2.7: 1, mixed and pressed into pellets, vacuum sealed in a glass tube and heated at 200 ° C. for 17 hours. The powder for a negative electrode was obtained by pulverizing to a powder of 200 mesh or less. This negative electrode powder and the styrene-butadiene-styrene block copolymer are kneaded in the same manner as in the case of the solid electrolyte sheet preparation, and the resulting mixture is drawn to evaporate toluene in dry air, 90% volume fraction,
A negative electrode sheet (negative electrode layer) having a thickness of 70 μm was obtained.

Further, the Cu powder and the TiS ₂ powder have a molar ratio of 0.1.
The mixture was mixed at a ratio of 5: 1, pressed into pellets, vacuum-sealed in a quartz tube, heated at 550 ° C. for 72 hours, and the obtained Cu _0.15 TiS ₂ pellets were pulverized to 200 mesh or less. The powder and a solid electrolyte powder composed of RbCu ₄ I _1.5 Cl _3.5 were mixed at a weight ratio of 1: 1 to obtain a positive electrode powder. The powder for positive electrode and the above-mentioned stinlene-butadiene-styrene block copolymer were kneaded and molded in the same manner as in the case of preparing the negative electrode sheet, and the volume fraction was 90.
%, A positive electrode sheet (positive electrode layer) having a thickness of 70 μm was obtained.

The obtained positive electrode sheet, solid electrolyte sheet, and negative electrode sheet were laminated in order, press-molded at 130 ° C. using a thin copper plate for the extraction electrode, and the periphery was sealed with an epoxy resin to prepare a battery.

FIG. 1 shows a sectional view of the obtained battery. In the figure, 1 is a solid electrolyte sheet, 2 is a positive electrode sheet, 3 is a negative electrode sheet, 4
Reference numerals 5 and 5 are extraction electrodes, and 6 is a sealing material. Table 1 shows the test results of the thickness, total conductivity, self-discharge characteristics, charge / discharge cycle, low temperature characteristics, and open circuit voltage of the obtained battery.

Furthermore, the bending resistance in a laminated state before resin sealing was also evaluated. The results are also shown in Table 1.

The total conductivity (s / cm) was obtained from the DC component by evaluating the impedance at an alternating current of 1 KH with an LCR meter (YHP427A manufactured by Yokogawa Hewlett-Packard Co.).

The self-discharge characteristics were obtained from the change in battery voltage during a charge / discharge cycle of 4 mAh / cc (2 hours discharge, 1 hour discharge).

The charging / discharging cycle was a charging / discharging cycle of 2.5 mAh / cc, and the discharging voltage was 0.35 V or less.

The low temperature characteristics are shown by the charge / discharge characteristics at -10 ° C.

The bending resistance was evaluated by conducting a bending test with a radius of 80 mm and evaluating the number of times the sheet was cracked or fractured.

Example 2 A solid electrolyte sheet (90% volume fraction of solid electrolyte powder in the mixture, 70 μm in thickness) was prepared in the same manner as in Example 1. As the negative electrode sheet, Cu powder, Cu ₂ S powder, and solid electrolyte powder composed of RbCu ₄ I _1.5 Cl _3.5 in a weight ratio of Cu: Cu ₂ S: RbCu ₄ I _1.5 Cl _3.5.
= 2.9: 2.7: 3 (negative electrode sheet (1), thickness 30μ
m) 2.9: 2.7: 2 (negative electrode sheet (2), thickness 30)
μm) and 2.9: 2.7: 1 (negative electrode sheet (3), thickness 30 μm) mixed in a ratio of 90%.
Were manufactured in the same manner as in Example 1. As the positive electrode sheet, a solid electrolyte powder composed of Cu _0.15 TiS ₂ powder and RbCu ₄ I _1.5 Cl _3.5 is used in a weight ratio of Cu _0.15 TiS ₂ : RbCu ₄ I _1.5 Cl _3.5 = 1:
3 (positive electrode sheet (1), thickness 30 μm), 1: 2 (positive electrode sheet (2), thickness 30 μm) and 1: 1 (positive electrode sheet
(3) A mixture having a thickness of 30 μm) was mixed in the same manner as in Example 1 so that the volume fraction was 90%.

The obtained sheets are laminated in the order of positive electrode sheet (3) / positive electrode sheet (2) / positive electrode sheet (1) / solid electrolyte sheet / negative electrode sheet (1) / negative electrode sheet (2) / negative electrode sheet (3), A battery was produced in the same manner as in Example 1 using a thin copper plate as the extraction electrode.
FIG. 2 shows a sectional view of the obtained battery. In the figure, 2a is a positive electrode sheet (1), 2b is a positive electrode sheet (2), 2c is a positive electrode sheet (3), 3a is a negative electrode sheet (1), 3b is a negative electrode sheet (2),
3c is a negative electrode sheet (3). The obtained battery was used in Example 1.
Tests were conducted in the same manner as above, and the results are shown in Table 1.

Example 3 A copper ion conductive solid electrolyte powder represented by RbCu ₄ I _1.75 Cl _3.25 obtained in the same manner as in Example 1 was used, and a styrene-ethylene-butylene-styrene block copolymer (SEBS) was used as a polymer elastic body. A solid electrolyte having a volume fraction of 90% and a thickness of 8
A solid electrolyte sheet of 0 μm was obtained.

Next, as a material for the electrode, a Cu suvrel compound powder represented by Cu ₂ Mo ₆ S _7.8 (average particle size = 2 μm) and RbCu were used.
₄ I _1.75 Cl _3.25 solid electrolyte powder in a weight ratio of 1:
The volume fraction of the mixture of 1 was 9 in the same manner as the solid electrolyte sheet.
An electrode sheet having a thickness of 0% and a thickness of 100 μm was obtained.

The obtained electrode sheet and solid electrolyte sheet were laminated in the order of the electrode sheet, the solid electrolyte sheet, and the electrode sheet, and a stainless steel plate having a thickness of 10 μm was used for the extraction electrode.
Press molding was carried out at 0 ° C., and the peripheral portion was sealed with an epoxy resin to prepare a battery having the structure of the cross section shown in FIG.

The battery thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 2.

Example 4 A copper ion conductive solid electrolyte powder represented by RbCu ₄ I _1.25 Cl _3.75 obtained in the same manner as in Example 1 and styrene-ethylene-butylene-styrene block copolymer (SEBS) as a polymer elastic body. Was kneaded in the same manner as in Example 1 and the resulting mixture was drawn and toluene was evaporated in dry air to obtain a solid electrolyte sheet having a volume fraction of 85% and a thickness of 65 μm. Next, Cu ₂ M as an electrode material
o ₆ S _7.8 copper suvrel compound powder (average particle size = 2 μm) and solid electrolyte powder consisting of RbCu ₄ I _1.25 Cl _3.75 in a weight ratio of 1: 1 and a basis weight of 10 g / m ² A positive electrode sheet having a volume fraction of 95% and a thickness of 100 μm was obtained in the same manner as the solid electrolyte sheet of Example 1 except that a polypropylene non-woven fabric of 80 μm was used. Further, a volume fraction of 95 was obtained in the same manner as in the positive electrode sheet, except that a Cu-Sbrell compound powder represented by Cu ₄ Mo ₆ S ₈ (average particle size = 2 μm) was used as an electrode material.
%, And a negative electrode sheet having a thickness of 100 μm was obtained. The obtained electrode sheet and solid electrolyte sheet were laminated in this order on the positive electrode sheet, the solid electrolyte sheet, and the negative electrode sheet, and a stainless steel plate having a thickness of 10 μm was arranged on the positive electrode side and a copper plate having a thickness of 10 μm was arranged on the negative electrode side as extraction electrodes. By press molding at 130 ° C. and sealing the peripheral portion with an epoxy resin to produce a battery having the same cross-sectional structure as shown in FIG. The battery thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 2.

Example 5 A copper ion conductive solid electrolyte powder represented by RbCu ₄ I _1.5 Cl _3.5 obtained in the same manner as in Example 1 and styrene-ethylene-butylene-styrene block copolymer (SEBS) as a polymer elastic body. Was kneaded in the same manner as in Example 1 and the resulting mixture was expanded and toluene was evaporated in dry air to obtain a solid electrolyte sheet having a volume fraction of 75% and a thickness of 55 μm. Next, the mixture was made to have a thickness of 200 including an activated carbon fiber which is a conductive mesh that also serves as an electrode material.
A woven cloth (specific surface area = 900 m ² / g) of μm was filled in the opening, sufficiently dried in a nitrogen stream to remove toluene, and the dry sheet had a solid electrolyte powder content of 20% by weight. An electrode sheet of 250 μm was obtained. The obtained electrode sheet and solid electrolyte sheet were laminated in the order of the electrode sheet, the solid electrolyte sheet, and the electrode sheet, a stainless steel plate having a thickness of 10 μm was arranged as a lead electrode, and press molding was performed at 130 ° C., and the peripheral portion was epoxy. An electric double layer capacitor having a cross-sectional structure similar to that shown in FIG. 1 was manufactured by sealing with a resin. The device thus obtained was tested in the same manner as in the battery of Example 1, and the results are shown in Table 2. However, the self-discharge characteristics were tested at 0.2 mAh / cc with the charging / discharging time being one-twentieth of that of the battery. The charge / discharge cycle is also 0.125 mAh / cc, which is one-twentieth.
I did it in.

Example 6 A copper ion conductive solid electrolyte powder represented by RbCu ₄ I _1.5 Cl _3.5 obtained in the same manner as in Example 1 and a styrene-butadiene-styrene block copolymer (SBS) as a polymer elastic body were used. Kneading in the same manner as in Example 1,
The obtained mixture was drawn and toluene was evaporated in dry air to obtain a solid electrolyte sheet having a volume fraction of 70% and a thickness of 55 μm. Next, the mixture was filled into an opening of a 200 μm-thick woven cloth (specific surface area = 900 m ² / g) made of activated carbon fiber which was a conductive mesh that also serves as an electrode material, and was sufficiently dried in a nitrogen stream. , Toluene was removed, and the content of the solid electrolyte powder in the dry sheet was 20% by weight and the thickness was 25.
A positive electrode sheet of 0 μm was obtained. On the other hand, Cu as an electrode material
₄ Mo ₆ S ₈ A copper shubrel compound powder (average particle size = 2 μm), a solid electrolyte powder having a weight ratio of 1: 1 and SBS were kneaded in the same manner as in Example 1. The obtained mixture was mixed with 200 μm of 100 μm in thickness.
The openings of the mesh copper net were filled to obtain a negative electrode sheet having a thickness of 110 μm and a volume fraction of the total amount of the solid electrolyte powder and the copper shubrel powder in the mixture of 95%. The obtained electrode sheet and solid electrolyte sheet are combined into a positive electrode sheet 2
One piece, a solid electrolyte sheet, and a negative electrode sheet are laminated in this order, and a stainless steel plate having a thickness of 10 μm is arranged on the positive electrode side and a brass plate having a thickness of 10 μm is arranged on the negative electrode side as an extraction electrode.
Press molding was carried out at 0 ° C., and the peripheral portion was sealed with an epoxy resin to produce an electric double layer capacitor having a structure of a cross section similar to that shown in FIG. The device thus obtained was tested in the same manner as in the battery of Example 1, and the results are shown in Table 2. However, the self-discharge characteristics were tested at 0.8 mAh / cc with the charging / discharging time being one-fifth that of the battery. The charge / discharge cycle is also 1/5, 0.5 mAh /
It was done with cc.

Example 7 H ₃ Mo ₁₂ PO _{40 having an} average particle size of 10 μm as a solid electrolyte
-H ⁺ ion conductive solid electrolyte powder represented by 29H ₂ O and styrene-butadiene-styrene block copolymer (SBS) were kneaded in the same manner as in Example 1, and the resulting mixture was used as Example 1. Similarly, it was filled into a nylon woven cloth to obtain a solid electrolyte sheet having a solid electrolyte volume fraction of 90% and a thickness of 80 μm. Next, the above mixture was applied to a thickness of 2 consisting of activated carbon fiber which is a conductive mesh that also serves as an electrode material.
The opening of a woven fabric of 00 μm (specific surface area = 900 m ² / g) was filled, dried sufficiently in a nitrogen stream to remove toluene, and the solid electrolyte powder in the dried sheet had a thickness of 20% by weight. A counter electrode sheet having a size of 250 μm was obtained. On the other hand, as a display material, tungsten trioxide (W
O ₃ ) and the solid electrolyte were dispersed in SBS in the same manner as in Example 1 so that the weight ratio was 1: 1 and kneaded, and the obtained mixture was spread and toluene was evaporated in the atmosphere. Thickness 8 with a volume fraction of the total amount of solid electrolyte powder and WO ₃ powder of 85%
A display electrode sheet of 0 μm was obtained.

The obtained display electrode sheet, counter electrode sheet, and solid electrolyte sheet were laminated in this order on the display electrode sheet, the solid electrolyte sheet, and the counter electrode sheet.
ITO of 0.3 μm thickness on m polyester sheet
A sheet having a transparent electrode is placed on the opposite side of a stainless steel plate having a thickness of 10 μm, press-molded at 80 ° C., and the periphery is sealed with an epoxy resin. The same cross section as shown in FIG. An electrochromic display device having the structure of was obtained. The device thus obtained was tested in the same manner as in the battery of Example 1, and the results are shown in Table 2. Further, when a color development-decolorization cycle test was carried out at 20 millicoulombs (mC) per unit device area, almost the same characteristics as the initial values were obtained even after 10 ⁵ times.

Although the case where a copper ion or a proton conductive solid electrolyte is used as the solid electrolyte has been described above, the same effect can be obtained by using other solid electrolytes such as silver ion conductivity, lithium ion conductivity and sodium ion conductivity. It goes without saying that you can get

〔The invention's effect〕

According to the solid electro-chemical element of the present invention, excellent ionic conductivity, processability, productivity, leaving stability and flexibility are excellent, and in the adhesion between the solid electrolyte layer and the electrode layer when manufacturing the element. It is excellent, and the device can be made thinner and the area can be increased.

[Brief description of drawings]

1 is a sectional view of a solid electrolyte battery according to Example 1 of the present invention, and FIG. 2 is a sectional view of a solid electrolyte battery according to Example 2 of the present invention. DESCRIPTION OF SYMBOLS 1 ... Solid electrolyte sheet, 2 ... Positive electrode sheet, 2a ... Positive electrode sheet (1), 2b ... Positive electrode sheet (2), 2c ... Positive electrode sheet
(3), 3 ... Negative electrode sheet, 3a ... Negative electrode sheet (1), 3b ... Negative electrode sheet (2), 3c ... Negative electrode sheet (3), 4 and 5 ... Extraction electrode, 6 ... Encapsulating material.

Front page continuation (72) Inventor Shigeo Kondo 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Tadashi Sotobe 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. References JP-A-58-123670 (JP, A)

Claims (5)

[Claims] 1. A solid electrolyte layer, and at least a pair of electrode layers joined to the upper and lower surfaces through the solid electrolyte layer,
A solid electrochemical element in which at least one of the solid electrolyte layer and the electrode layer is a sheet-like molded body using a mesh body as a carrier, and the solid electrolyte layer is a mixture in which solid electrolyte powder is dispersed in a polymer elastic body. At least one of the electrode layers contains solid electrolyte powder or a mixture of solid electrolyte powder and electrode material powder dispersed in a polymer elastic body, and the polymer elastic body is a styrene-butadiene-styrene block. At least one of a copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer and 1,2-polybutadiene, and at least one of the solid electrolyte layer and the electrode layer. Solid state electrification, characterized in that the mixture is filled in the openings of the mesh body. Element. 2. A solid electrolyte layer comprising a mixture of solid electrolyte powder dispersed in a polymer elastic body at a volume fraction of 55 to 95%.
The solid electrochemical device according to claim 1, which is a sheet-shaped molded body obtained by filling the openings of the non-conductive mesh body. 3. An electrode layer is filled with a mixture of an electrode material powder and, if necessary, a solid electrolyte powder dispersed in a polymer elastic body at a volume fraction of 75 to 95%, and filling the opening of a mesh body. The solid electrochemical element according to claim 1 or 2, characterized in that 4. The electrode layer is formed by filling a mixture in which a solid electrolyte powder is dispersed in a polymer elastic body into an opening of a conductive reticulate body which also serves as an electrode material. The solid-state electrochemical device according to item 1 or 2. 5. The electrode layer is formed by stacking a plurality of sheets in which the mixing ratio of the electrode material powder and the solid electrolyte powder is changed step by step, in the order of the mixing ratio, and the mixing ratio of the solid electrolyte powder is large. The solid electrochemical element according to any one of claims 1 to 3, wherein the electrode layer surface is joined to the solid electrolyte layer.