JPH01657A - solid state electrochemical device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a solid-state electrochemical device, and more particularly, to a solid-state electrochemical device used in solid-state batteries, solid-state electric double layer capacitors, solid-state electrochromic displays, etc. .

[Conventional technology]

Solid-state electrochemical devices have the advantage that all of their material components are solid substances, so there is no liquid leakage, and they can be easily made smaller and thinner. When constructing such an element,
A solid state ion conductor, that is, a solid electrolyte layer, is required to move ions inside the device. The solid electrolytes are classified by mobile ion species, and include Li + ion conductive solid electrolytes, Ag + ion conductive solid electrolytes, Cu + ion conductive solid electrolytes, H + ion conductive solid electrolytes, and the like. A solid electrochemical device is constructed by combining the solid electrolyte and an electrode material, and a pair of electrode layers is usually arranged on the upper and lower surfaces of solid electrolyte powder that has been pressure-pressed into layers.

In electrochemical devices that use liquid electrolytes, electrical and ionic bonding between the electrolyte and electrode materials is easy, whereas in solid electrochemical devices that use solid materials, solid electrolytes can be bonded to each other, electrode materials to each other, or solid electrolytes and electrodes. Electrical and ionic bonding with materials is generally difficult. In devices that use liquid electrolytes, the electrolyte or electrodes are mixed with adhesives or other impurities to prevent the electrolyte from flowing out or to prevent the electrolyte from penetrating into the electrodes too much and causing the electrodes to lose their shape. . However, in solid-state electrochemical devices, inclusion of impurities makes electrical and ionic bonding more difficult, so inclusions cannot be used. therefore,
When producing solid electrochemical devices using solid electrolytes and electrode materials, which are inorganic solid powders, it is necessary to pelletize them using a high-pressure press, and the resulting pellets are hard and brittle, resulting in problems with productivity, uniformity, etc. This is a major obstacle in obtaining the In other words, when joining an electrode material and a solid electrolyte, it is necessary to bring them into close contact with each other under great pressure.
In the case of a large-area solid electrochemical device, it is difficult to obtain uniform adhesion, and if too much pressure is applied, problems such as damage to the solid electrolyte layer and causing internal short circuits occur.

[Problem that the invention seeks to solve]

An object of the present invention is to solve the problems of the prior art as described above, to achieve a thinner design and larger area, to facilitate the handling of element constituent materials, and to improve processability and productivity during element assembly. The purpose of the present invention is to provide an excellent solid-state electrochemical device.

[Means for solving problems]

The present invention provides a solid electrochemical element having a solid electrolyte layer and at least a pair of electrode layers joined to upper and lower surfaces via the solid electrolyte layer, in which the solid electrolyte layer and/or the electrode layer is made of solid electrolyte powder. and/or a sheet-like molded body formed by filling the openings of a net-like body with the mixture in which electrode material powder is dispersed in an elastic polymer body.

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

The solid electrochemical device thus obtained is easy to manufacture, has flexibility, and can be easily manufactured to be thin and have a large area.

The solid electrolyte powder used in the present invention includes Lif, L
iI・H2O5Li3N-Li4Si04-L i3
Li” ion conductive solid electrolyte such as PO4, RbAg4
Ishi, KAg4Iji, Ag3 S! , Ag l-Ag
20-Ag1 ion conductive solid electrolyte such as MoO3 glass, RbCu412-^(13+x(X=0.2~0
．． 6), CuJ-Cu20-M.

Cu+ ion conductive solid electrolyte such as 03 glass, H3M
Ot2PO+o・29H20, H3W12 P 040
・H+ ion conductive solid electrolyte such as 29H20, sodium beta alumina (Na-β-A1203),
Nat+aZr2 p,, -Q s i, o
12 (a=O~3) l'Ja+ ion conductive solid electrolyte, etc. can be mentioned.

° Among these solid electrolytes, Rbcu411. '1
rC13,2'; , RbCu4 11. ! 1
c13. ys RbCu4 11. xiC13,
1? Rb such as r Cu 412-X Cl 3+X
The Cu+ ion conductive solid electrolyte represented by (X = 0°2 to 0.6) has a high ion conductivity of 10-2 s/cm at room temperature and is particularly preferred.

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

In addition, when electrode material powder and solid electrolyte powder are present in the electrode layer, the ratio of electrode material powder/solid electrolyte powder is l/4 to
5/4 (weight ratio) is preferred.

As the polymer elastic body used in the present invention, for example, 1
, 4-polybutadiene, natural rubber, polyisoprene, S
BR,, NBR, EPDM, EPM.

Urethane rubber, polyester rubber, chloroprene rubber, epichlorohydrin rubber, silicone rubber, styrene-butadiene-styrene block copolymer (S B S
), styrene-isoprene-styrene pro-7 copolymer (STS), styrene-ethylene-butylene-styrene block copolymer <5EBS), butyl rubber, phosphazene rubber, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polystyrene, Vinyl chloride, ethylene-ethyl acetate copolymer, 1
゜2- Electrically insulating polymeric elastomers such as polybutadiene, epoxy resin, phenol resin, cyclized polybutadiene, cyclized polyisoprene, polymethyl methacrylate, and mixtures thereof are mentioned, but electrode material powder, solid electrolyte powder and In terms of adhesion, SBS, SIS, 5RBS, 1.2
- Thermoplastic materials such as polybutadiene are preferred, and from the viewpoint of flexibility, those with an ASTM-A hardness of 90 or less are preferred. Also, from the point of view of the heat resistance of solid electrolyte powder,
It is preferable that the material has moldability at 50° C. or lower.

As the solid electrolyte layer in the present invention, a mixture in which solid electrolyte powder is uniformly dispersed in an elastomer polymer preferably at a volume fraction of 55 to 95%, more preferably 75 to 92% is used as a non-conductive network layer. It is preferable to use an electrolyte sheet filled in the openings of the electrolyte sheet.

When the volume fraction of solid electrolyte powder is less than 55%, the ionic conductivity is 1/1000 to 1/10,000 compared to the powder state.
RbCu412-x C1 has the highest conductivity.
Even in the 3+x system, I X 10-6s is 7cm or less,
In addition, if the volume fraction exceeds 95%, when forming a sheet,
The resulting solid electrolyte sheet may be brittle and easily fall off.

The electrode layer in the present invention preferably contains electrode material powder and solid electrolyte powder in a volume fraction of 75 to 75% in a polymer elastic body.
An electrode layer is formed by filling the openings of a conductive network with a mixture dispersed at a volume fraction of 95%, or a solid electrolyte powder is dispersed in a polymer elastic body at a volume fraction of preferably 55 to 95%. Preferably, the electrode layer is formed by filling the openings of a conductive network that also serves as an electrode material with a dispersed mixture. If the volume fraction is less than 75%, the contact efficiency between the electrode material powder and the solid electrolyte powder in the electrode layer will decrease, making it impossible to obtain sufficient polarization characteristics as an electrode, and if the volume fraction exceeds 95%, the sheet will deteriorate. When it oxidizes, it may become brittle and fall off easily.

In addition, the electrode layer in the present invention is made by laminating a plurality of sheets in which the mixing ratio of electrode material powder and solid electrolyte powder is changed in stages, in order of the mixing ratio, so that the surface of the electrode layer with a larger mixing ratio of solid electrolyte powder is the solid electrolyte. It is preferable to bond with the layer.

The shape and particle size of the solid electrolyte powder and electrode material powder used in the present invention are not particularly limited, but from the viewpoint of ease of mixing with the polymeric elastomer, etc. Those that pass through a sieve are preferred.

The method of uniformly dispersing solid electrolyte powder and/or electrode material powder in an elastomer polymer to obtain a solid electrolyte mixture or a mixture for an electrode layer is not particularly limited, Examples include a method of kneading a polymer solution dissolved in a specific solvent with solid electrolyte powder, electrode material powder, etc. using a ball mill or the like. This method generates less heat during kneading and is unlikely to cause deterioration or decomposition of the solid electrolyte powder, electrode material powder, etc. Furthermore, there is almost no contact with the atmosphere during cross-talk, so the deterioration or decomposition of the powder due to moisture, oxygen, etc. It is preferable as a manufacturing method because it is difficult to control and there is no need to particularly adjust conditions such as ambient temperature and oxygen.

Examples of solvents used in this case include n-hexane, n-hebutane, n-octane, cyclohexane, benzene, toluene, xylene, ethyl acetate, and trichlene, which are non-water absorbing and do not react with the solid electrolyte powder or electrode material powder. It is preferable to use a saturated hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent or an ester solvent.

Examples of the material for 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,
Examples include conductive materials such as titanium and stainless steel, and specific examples of the net-like body include woven fabrics and non-woven fabrics made of these materials. The aperture ratio of these net-like bodies is suitably in the range of 35 to 65%. The aperture ratio is determined by the ratio of the total aperture area per unit area of the reticular body.

If the aperture ratio is less than 35%, if it is a solid electrolyte layer,
The electrical conductivity is small (the polarization becomes large when used as an electrode layer), and if the aperture ratio exceeds 65%, the strength cannot be maintained as a layer, which is undesirable. A range of 50 to 1000 rrf/g is appropriate.Furthermore, in the case of nonwoven fabric, the basis weight is 5 to 50 glc
A range of d is appropriate. The thickness of the network is 10 to 150 μm for a non-conductive network, and 30 to 30 μm for a conductive network, taking into account the strength of the network itself and the thinning of the device.
The range is preferably 0 μm, the average area per opening is preferably 1.6×10 −3 to 9×10 −2 nd, and the width between adjacent openings is preferably 20 to 120 μm.

As a method for filling the openings of the net-like body with the solid electrolyte layer mixture or the electrode layer mixture, for example, the net-like body is immersed in a slurry in which the mixture is dispersed in a solvent, and the mixture is sufficiently poured into the net-like body. After adhesion, a method of filling the opening with a blade, roll, or the like made of hard rubber, plastic, metal, etc. and removing excess adhesion of the mixture can 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 openings of the net with the mixture in this way,
For example, the solid electrolyte layer and electrode layer used in the solid electrochemical device of the present invention can be obtained by drying at 20 to 30° C., preferably in an inert gas atmosphere. Note that these layers are formed by filling the openings of the mesh with a mixture of solid electrolyte powder, electrode material powder, polymeric elastomer, etc.; In order to improve adhesion, conductivity, polarizability, capacity, etc.
It is preferable that the mixture layer has a thickness of 5 to 25 μm on either or both the upper and lower sides of the net-like body.

According to the above method, it is possible to obtain a solid electrolyte layer or an electrode layer with extremely excellent thickness accuracy because the network is used as a base material, and since these can be manufactured continuously, a large-sized 1III layer can be obtained. can be obtained easily. Therefore, a solid electrochemical device with a large area, thin shape, and uniform thickness can be easily obtained.

Further, the thickness of the solid electrolyte layer and the electrode layer is 10
~250 μm is preferred.

For example, modified rosin, rosin derivative, terpene resin, coumaron-indene resin, phenol-modified coumaron-indene resin, etc. are added to the solid electrolyte layer and electrode layer of the present invention in order to increase the adhesive strength with each layer. It may contain a rosin tackifier, an aromatic tackifier or a terpene tackifier.

The solid electrolyte powder or polymeric elastomer contained in the solid electrolyte layer and the electrode layer may be the same or different, but from the viewpoint of homogeneity of the molded body, adhesiveness between the solid electrolyte layer and the electrode layer, etc. 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 adhesion with the electrode layer, a thin copper plate is used in the case of a copper-based electrode layer, and a silver plate is used in the case of a silver thread electrode layer. A thin plate is preferred, but it may also be a thin copper plate plated with nickel or gold, or an alloy such as phosphor bronze.

In the present invention, in the electrode layer, the mixing ratio of the solid electrolyte powder and the electrode material powder is gradually changed from the surface in contact with the solid electrolyte layer, and the ratio of solid electrolyte powder is thicker on the surface in contact with the solid electrolyte layer. It is preferable to form a multilayered electrode layer in which a plurality of sheets are laminated in the order of mixing ratio so that the ratio of solid electrolyte powder decreases as one approaches the electrode.In this case, the degree of multilayering of the electrode layer is particularly determined by Although there is no limitation and it is effective even with 2 layers, it is preferably 3 to 9 layers.However, from the viewpoint of avoiding complicated processing and thickening, 3 to 9 layers are effective.
Six layers is appropriate. By multilayering the electrode layer in this way, the effect of reducing the interfacial 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 exchanges ions with the solid electrolyte, such as titanium disulfide or copper shuvrel. By using a solid electrolyte and an electrode material that undergoes optical change by electrochemically transferring ions to and from the solid electrolyte, such as tungsten oxide, it is possible to create a solid electrochemical display element (electrochromic display). . Furthermore, a solid electric double capacitor can be formed by using the solid electrolyte and an electrode material such as activated carbon, which does not exchange ions with the solid electrolyte but forms an electric double layer at the interface with the solid electrolyte. .

According to the present invention, such a solid electrochemical element also has excellent flexibility and is extremely resistant to mechanical shock.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 CuC1! , CuI and RhCl1 in molar ratio Cu
cl:CuI:RbCjt=2.5:1
．． Each sample was weighed at a ratio of 5:1.

The CuC1 and CuI were recrystallized in hydrochloric acid and were converted to p2 o! On the other hand, the above RbC1 was vacuum dried at 100°C, a predetermined amount of these component salts were mixed, heated at 130°C for 17 hours to completely dehydrate, and this was dried in Pyrex. Vacuum sealed in a glass tube, melted, cooled slowly to room temperature, and solidified using a ball mill using toluene as a dispersant. After processing for about 17 hours, the obtained pressure molded product was ground again in a ball mill to obtain RbCu411.5CI135.
A powder was obtained.

Next, 1 part (parts by weight, same hereinafter) of styrene-butadiene-styrene block copolymer (specific gravity: 0.96, manufactured by Japan Synthetic Rubber Co., Ltd., TR-2000) as a polymeric elastomer was dissolved in toluene to dissolve the polymer. A solution was obtained, and to this was added 4.22 parts of Rb Cu411.5Cl with a particle size of 200 mesh or less.
A solid electrolyte powder of 3.5 fJ· (specific gravity: 4.5) was added and kneaded in a ball mill for 2 hours, and the resulting mixture was transferred to a polyethylene container and the solid content concentration was adjusted to 79% by weight. On the other hand, a nylon woven fabric with a thickness of 50 μm, an average area per opening of 5°5XIQ-3 mm, and a width of 50 μm between adjacent openings was used as the woven fabric, and this woven fabric was immersed in the mixture in a polyethylene container. After applying the mixture to the surface of the woven fabric, the woven fabric is sandwiched between fluoro rubber blades, and while applying sufficient clamping force, the woven fabric is pulled out from the blade, and the mixture is applied to the opening of the woven fabric. Filled. The obtained sheet was sufficiently dried in a nitrogen stream to remove toluene, and a solid electrolyte sheet having a volume fraction of solid electrolyte powder in the mixture of 90% and a thickness of 70 μm was obtained.

Next, Cu powder, Cu2S powder and RbCu4
Solid electrolyte powder consisting of 1t, sc 13j in weight ratio Cu: Cu2 S: RbCu< It, 5C1
3. Mix at a ratio of s=2.9:2.7:1, press mold into a pellet, and vacuum seal in a glass tube.
The pellets were heated at .degree. C. for 17 hours and pulverized into a powder of 200 mesh or less to obtain a powder for a negative electrode. This negative electrode powder and the styrene-butadiene-styrene block copolymer are kneaded in the same manner as in the case of producing the solid electrolyte sheet, the resulting mixture is stretched, and the toluene is evaporated in dry air, A negative electrode sheet (negative electrode layer) having a volume fraction of 90% and a thickness of 70 μm was obtained. .

In addition, the molar ratio of Cu powder and TiS2 powder is 0.15.
: Mixed in a ratio of 1:1 and press-molded into pellets, vacuum sealed in a quartz tube and heated at 550°C for 72 hours, the resulting Cu6.1zT i S 2 pellets were crushed to a size of 200 mesh or less. This powder and RbCu411
．． Solid electrolyte powder consisting of 5C13,S in a weight ratio of 1:l
were mixed to obtain a positive electrode powder. This positive electrode powder and the above-mentioned styrene-butadiene-styrene block copolymer were kneaded and molded in the same manner as in the case of producing the negative excavation sheet, and a positive electrode sheet with a volume fraction of 90% and a thickness of 70 μm (positive electrode layer) 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 copper thin plate as an extraction electrode, and the peripheral portion was sealed with epoxy resin to produce a battery.

FIG. 1 shows a cross-sectional view of the obtained battery. In the figure, l is a solid electrolyte sheet, 2 is a positive electrode sheet, 3 is a negative electrode sheet, 4
5 is an extraction electrode, and 6 is a sealing material. Table 1 shows the test results for 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 the laminated state before resin sealing was also evaluated. The results are also shown in Table 1.

The total conductivity (S 2 /am) was determined by evaluating the impedance at AC lKH2 using an LCR meter (YHP427A, manufactured by Yokogawa Hewlett-Packard) and from its DC component.

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

The charge/discharge cycle was a charge/discharge cycle of 2.5 mAh/cc, and was expressed as the number of cycles at which the discharge voltage became 0.35 volt or less.

The low-temperature characteristics were shown as charge-discharge characteristics at -10°C.

The bending resistance was evaluated by performing a bending test at a radius of 80 mm and counting the number of times the sheet cracked or broke.

Example 2 A solid electrolyte sheet (volume fraction of solid electrolyte powder in the mixture: 90%, thickness: 70 μm) was produced in the same manner as in Example 1. As the negative electrode sheet, Cu powder, Cu2S powder and Rb Cu4I 1. Solid electrolyte powder consisting of HC13 and E was prepared in a weight ratio of Cu:Cu2S:
RbCu4 fJc13s=2.9: 2.7:
3 (negative electrode sheet (1), thickness 3 (lljm), 2.
9:2.7:2 (negative electrode sheet (2), thickness 30μ
m) and 2.9:2.7:1 (negative electrode sheet (3), thickness 30 μm) with a volume fraction of 90%.
Each was produced in the same manner as in Example 1 so that the following results were obtained. In addition, as a positive electrode sheet, Cu6.15T i S
A solid electrolyte powder consisting of CuoasTis2 powder, Rbcu41i, and sC7!3.5 was prepared in a weight ratio of CuoasTis2:RbC
u4 It, 5C13,5=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), thickness 30 μm)
[mu]m) were mixed in the same manner as in Example 1 so that the volume fraction was 90%.

The obtained sheet was made into positive electrode sheet (3) / positive electrode sheet (2
)/Cathode sheet [1)/Solid electrolyte sheet/Negative electrode sheet (
A battery was produced in the same manner as in Example 1 by laminating 7 in the order of 1)/negative electrode sheet (2)/negative electrode sheet (3) and using a thin copper plate as the lead electrode. FIG. 2 shows a cross-sectional view of the obtained battery. In the figure, 2a is the positive electrode sheet 1- (1), 2b is the positive electrode sheet (2), 2C is the positive electrode sheet (3), 3a is the negative electrode sheet (1), 3b is the negative electrode sheet (2), 3C is the negative electrode sheet H3 ). The obtained battery was tested in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 Example 3 RbCu411. obtained in the same manner as Example 1. q5Cff
A solid electrolyte was prepared in the same manner as in Example 1, except that a copper ion conductive solid electrolyte powder represented by i 3.25 was used and a styrene-ethylene-butadiene-styrene block copolymer (SEBS) was used as the polymeric elastomer. A solid electrolyte sheet with a thickness of 80 μm and a volume fraction of 90% was obtained.

Next, use Cu2Mo6s as an electrode material. ,? Copper Shubrel compound powder (average particle size = 2 μm) represented by R
bCu411. An electrode sheet having a volume fraction of 90% and a thickness of 100 μm was obtained by using a mixture of solid electrolyte powder consisting of q5Cl13.25 with an M ratio of 1=1 in the same manner as the solid electrolyte sheet.

The obtained electrode sheet and solid electrolyte sheet were laminated in the order of electrode sheet, solid electrolyte sheet, and electrode sheet, and a stainless steel plate with a thickness of 10 μm was used as the extraction electrode.
Press molded at 0°C and sealed with epoxy resin around the periphery.
A battery having the cross-sectional structure shown in FIG. 1 was manufactured.

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

Example 4 RbCu4If,25C obtained in the same manner as Example 1
f3. A mixture obtained by kneading copper ion conductive solid electrolyte powder represented by 7 g and styrene-ethylene-butadiene-styrene block copolymer (SEBS) as a polymeric elastomer in the same manner as in Example 1. was stretched and the toluene was evaporated in dry air until the volume fraction was 85.
A solid electrolyte sheet with a thickness of 65 μm was obtained. Next, Cu2Mo6S7. Copper Shubrel compound powder (average particle size = 2.um) expressed in g and RbCu41
The solid electrolyte sheet of Example 1 was used, except that a mixture of solid electrolyte powder consisting of s, xs C5, qs at a weight ratio of 1:1 was used, and a polypropylene nonwoven fabric with a thickness of 80 μm and a basis weight of 10 g/cd was used. Similarly, the volume fraction is 95%
A positive electrode sheet having a thickness of 100 μm was obtained. Further, a negative electrode sheet having a volume fraction of 95% and a thickness of 100 μm was obtained in the same manner as the positive electrode sheet except that a copper shuvrel compound powder represented by Cu2Mo6S7 (average particle size = 2 μm) was used as the electrode material. The obtained electrode sheet and solid electrolyte sheet were laminated in the order of positive electrode sheet, solid electrolyte sheet, and negative electrode sheet, and a thickness of 10 μm was formed on the positive electrode side as an extraction electrode.
A battery with a cross-sectional structure similar to that shown in Figure 1 was made by press-molding a stainless steel plate at 130°C with a 10 μm thick copper plate placed on the negative electrode side and sealing the periphery with epoxy resin. was created. The obtained battery was tested in the same manner as in Example 1, and the results are shown in Table 2.

Example 5 R b Cu 411. obtained in the same manner as in Example 1. sC
A copper ion conductive solid electrolyte powder represented by l 3.5 and a styrene-ethylene-butadiene-styrene block copolymer (SEBS) as a polymeric elastomer were kneaded in the same manner as in Example 1 to obtain a The mixture was stretched and the toluene was evaporated in dry air to obtain a solid electrolyte sheet with a volume fraction of 75% and a thickness of 55 μm.Next, the mixture was spread over activated carbon, which is a conductive network that also serves as an electrode material. A woven fabric made of fibers with a thickness of 200 μm (specific surface area = 900
rrr/g) and was thoroughly dried in a nitrogen stream to remove toluene to obtain a 250 μm thick electrode sheet with a solid electrolyte powder content of 20% by weight in the dried sheet. The obtained electrode sheet and solid electrolyte sheet were
The electrode sheet, solid electrolyte sheet, and electrode sheet were laminated in this order, and a stainless steel plate with a thickness of 10 μm was placed as an extraction electrode, press-molded at 130°C, and the peripheral part was sealed with epoxy resin, as shown in Figure 1. An electric double layer capacitor with a cross-sectional structure similar to that of the above was fabricated. The obtained device was tested in the same manner as the battery of Example 1, and the results are shown in Table 2. However, the self-discharge characteristic is 0.2 mA h / 1/20th of the charging and discharging time of a battery.
A test was conducted at cc. The charge/discharge cycle is also 2
It was performed at 0.125 mA h/cc, which is 1/0.

Example 6 R b Cu 41 s,s obtained in the same manner as Example 1
A copper ion conductive solid electrolyte powder represented by C13,s and a styrene-butadiene-styrene block copolymer (SBS) as a polymeric elastomer were kneaded in the same manner as in Example 1, and the resulting mixture was mixed. Stretch and evaporate toluene in dry air to a thickness of 55 μm with a volume fraction of 70%.
A solid electrolyte sheet was obtained.

Next, the mixture is filled into the openings of a 200 μm thick woven fabric (specific surface area = 900 m/g) made of activated carbon fibers, which is a conductive network that also serves as an electrode material, and thoroughly dried in a nitrogen stream. Toluene was removed to obtain a positive electrode sheet having a solid electrolyte powder content of 20% by weight and a thickness of 250 μm in the dried sheet. On the other hand, Cu4Mo63B is used as an electrode material.
Copper Shubrel compound powder expressed as (average particle size = 2μ
m), the solid electrolyte powder in a weight ratio of 1:1, and SBS were kneaded in the same manner as in Example 1. A negative electrode sheet having a thickness of 110 μm and having a volume fraction of the total amount of solid electrolyte powder and copper Chevrel powder in the mixture of 95% was obtained. The obtained electrode sheet and solid electrolyte sheet were laminated in the order of two positive electrode sheets, a solid electrolyte sheet, and a negative electrode sheet, and a 10 μm thick stainless steel plate was used as an extraction electrode on the positive electrode side and a 10 μm thick stainless steel plate on the negative electrode side. Brass plates were arranged and press-molded at 130° C., and the periphery was sealed with epoxy resin to produce an electric double layer capacitor having a cross-sectional structure similar to that shown in FIG. The obtained device was tested in the same manner as the battery of Example 1, and the results are shown in Table 2. However, for self-discharge characteristics, the charging and discharging time was reduced to one-fifth of that of a battery, and a test was conducted at 0.8 mAh/cc. Similarly, the charge/discharge cycle is 1/5th of 0.5 mA h/
It was done in cc.

Example 7 H3Mo12po with an average particle size of 10 μm as a solid electrolyte
H4 ion conductive solid electrolyte powder represented by 4o.29H20 and styrene-butadiene-styrene block copolymer (SBS) were kneaded in the same manner as in Example 1,
The obtained mixture was filled in a nylon woven fabric in the same manner as in Example 1 to a thickness of 80 μm with a solid electrolyte volume fraction of 90%.
A solid electrolyte sheet of m was obtained. Next, the mixture is filled into the openings of a 200 μm thick woven fabric (specific surface area = 900 rrr/g) made of activated carbon fibers, which is a conductive network that also serves as an electrode material, and thoroughly dried in a nitrogen stream. Toluene is removed and the content of solid electrolyte powder in the dry sheet is reduced to 2.
A counter electrode sheet having a thickness of 250 μm and containing 0M amount % was obtained. on the other hand,
As a display material, tungsten dioxide (WO3) with an average particle size of 8 μm and the solid electrolyte were dispersed in SBS at a weight ratio of 1:1 and kneaded, and the resulting mixture was mixed. After stretching, toluene was evaporated in the atmosphere to obtain a display electrode sheet having a thickness of 80 μm and having a total volume fraction of solid electrolyte powder and WO3 powder of 85%.

The obtained display electrode sheet, counter electrode sheet, and solid electrolyte sheet were laminated in the order of display electrode sheet, solid electrolyte sheet, and counter electrode sheet, and a thickness of 50 μm was formed on the display electrode side as an extraction electrode.
ITO with a thickness of 0.3μm on a polyester sheet with a thickness of 0.3μm
A sheet provided with a transparent electrode was press-molded at 80°C with a 10 μm thick stainless steel plate placed on the counter electrode side, and the periphery was sealed with epoxy resin to form a cross section similar to that shown in Figure 1. An electrochromic display element having the structure was obtained. The obtained device was tested in the same manner as the battery of Example 1, and the results are shown in Table 2.

Further, when a coloring-decoloring cycle test was carried out at 20 millicoulombs (mC) per unit device area, characteristics almost unchanged from the initial state were obtained even after 10" cycles were carried out once.

Table 2 above shows cases in which a copper ion or proton conductive solid electrolyte is used as the solid electrolyte, but other solid electrolytes such as silver ion conductivity, lithium ion conductivity, sodium ion conductivity, etc. may also be used. Needless to say, similar effects can be obtained.

〔Effect of the invention〕

According to the solid electrochemical device of the present invention, it has excellent ionic conductivity, and is also excellent in processability, productivity, storage stability, and flexibility, and has excellent adhesion between the solid electrolyte layer and the electrode layer when manufacturing the device. This makes it possible to make the device thinner and larger in area.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view of a solid electrolyte battery according to Example 1 of the present invention, and FIG. 2 is a cross-sectional view of a solid electrolyte battery according to Example 2 of the present invention. 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), 3 c-...Negative electrode sheet (3), 4 and 5...
- Extraction electrode, 6... sealing material. Agent Patent Attorney Takeshi Kawakita 1: Solid electrolyte sheet 2a: Positive electrode sheet (1) 2b = Positive electrode sheet (2) (2C: Positive electrode sheet (3).

Claims (5)

[Claims] (1) In a solid electrochemical device having a solid electrolyte layer and at least a pair of electrode layers joined to the upper and lower surfaces via the solid electrolyte layer, the solid electrolyte layer and/or the electrode layer are made of solid electrolyte powder and 1. A solid electrochemical device, characterized in that it is a sheet-like molded body formed by filling the openings of a mesh body with a mixture in which electrode material powder is dispersed in an elastic polymer body. (2) The solid electrolyte layer is a sheet-like molded body formed by filling the openings of a non-conductive network with a mixture in which solid electrolyte powder is dispersed in a polymer elastic body at a volume fraction of 55 to 95%. A solid electrochemical device according to claim 1, characterized in that: (3) The electrode layer is formed by filling the openings of the network body with a mixture in which electrode material powder and solid electrolyte powder are dispersed at a volume fraction of 75 to 95% in an elastic polymer body. A solid electrochemical device according to claim 1 or 2, characterized in that: (4) Claim 1, characterized in that the electrode layer is formed by filling the openings of a conductive network that also serves as an electrode material with a mixture of solid electrolyte powder dispersed in an elastomer polymer. The solid electrochemical device according to item 1 or 2. (5) The electrode layer is made by laminating a plurality of sheets in which the mixing ratio of electrode material powder and solid electrolyte powder is changed in stages, and the electrode layer side has a large mixing ratio of solid electrolyte powder. 4. The solid electrochemical device according to claim 1, wherein the solid electrochemical device is bonded to a solid electrolyte layer.