KR20070032274A - Ion conductor and electrochemical display device utilizing the same - Google Patents

Abstract

The present invention relates to an ion conductor and an electrochemical display device using the same.

Ion conductors used between electrodes such as electrochemical display elements are required to have both high ion conductivity and a function as a separator. Although a polymer gel electrolyte is known as such an ion conductor, from the standpoint of compatibility between an organic polymer that is an electrolyte holder and a solvent of an electrolyte solution, the type of solvent of the electrolyte solution is limited depending on the type of organic polymer used. There was a problem.

The present invention consists of fine particles of an organic polymer containing 20 to 80% by mass of ultrafine particles of an inorganic compound and an electrolyte solution impregnated in the organic polymer fine particles, and the ultrafine particles of the inorganic compound have an average of 500 nm or less. The above problem is solved by using an ion conductor having a particle diameter and a fine particle of an organic polymer having a specific surface area by a BET method of 30 m ² / g or more.

Ion conductor, electrochemical display device

Description

ION CONDUCTOR AND ELECTROCHEMICAL DISPLAY DEVICE UTILIZING THE SAME}

The present invention relates to an ion conductor and an electrochemical display device using the same.

As a member used between electrodes, such as a battery and an electric double layer capacitor (electric double layer capacitor), the structural material which prevents the short circuit between electrodes is unnecessary, and the solid material which has no possibility of leaking electrolyte solution is developed. The materials used in these materials are required to have a high level of two functions: high ion conductivity as an ion conductor, structural stability as a separator, and processability. As such materials, intrinsic polymer electrolytes (all solid types) and polymer gel electrolytes are known.

However, intrinsic polymer electrolytes are basically low in ionic conductivity (less than 10 ⁻⁴ S / cm at room temperature), and thus, intrinsic polymer electrolytes used at room temperature have not yet been put to practical use.

The polymer gel electrolyte may be a homogeneous gel electrolyte in which organic polymers such as polyethylene oxide, polyacrylonitrile, and polyvinylidene fluoride are swelled in accordance with an electrolyte solution in which a supporting electrolyte (LiC10 ₄ , quaternary ammonium salt, etc.) is dissolved in a polar solvent. (See, for example, Patent Documents 1 and 2), a structural gel electrolyte in which an organic polymer such as polyolefin, polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride is used as a porous body, and the electrolyte solution is held in the micropores of the porous body ( For example, patent documents 3 and 4), and the thing in which the electrolyte was impregnated to the network support which consists of a polymer which does not have electronic conductivity (for example, refer patent document 5) can be illustrated.

The homogeneous gel electrolyte is less likely to leak the electrolyte solution, but the electrolyte retention amount is about five times that of the organic polymer even at the maximum, so that the ion conductivity is low and does not reach the ion conductivity of the electrolyte alone. On the other hand, the structure-type gel electrolyte has a problem that electrolyte solution is easy to leak. In addition, both of them had a problem that the kind of the solvent of the electrolyte solution was limited depending on the kind of the organic polymer used from the viewpoint of compatibility between the organic polymer as the electrolyte holder and the solvent. For this reason, there is a demand for an ion conductor having a high retention rate in any electrolyte solution and less likely to leak.

Patent Document 1: Japanese Patent Application Laid-Open No. 2001-351832

Patent Document 2: Japanese Patent Application Laid-Open No. 11-149825

Patent Document 3: International Publication No. 95/06332 Pamphlet

Patent Document 4: International Publication No. 95/15589 Pamphlet

Patent Document 5: Japanese Patent Application Laid-Open No. 2000-11758

[Initiation of invention]

[Problem to Solve Invention]

An object of the present invention is to provide an ion conductor which can increase the amount of the impregnation of the electrolyte, regardless of the type of solvent of the electrolyte or the concentration of the supporting electrolyte, thereby increasing the ion conductivity and preventing the impregnated electrolyte from leaking. It is done.

[Means for solving the problem]

The present inventors have found that an ion conductor containing a large amount of ultra fine particles of an inorganic compound having an average particle diameter of 500 nm or less and impregnated with an electrolytic solution in fine particles of an organic polymer having a large specific surface area by the BET method, satisfies the above problems. The present invention has been completed.

That is, the present invention is composed of fine particles of an organic polymer containing 20 to 80% by mass of ultrafine particles of an inorganic compound and an electrolyte solution impregnated into fine particles of the organic polymer, wherein the ultrafine particles of the inorganic compound have an average particle diameter of 500 nm or less. The present invention provides an ion conductor in which the fine particles of the organic polymer have a specific surface area by a BET method of 30 m ² / g or more.

[Effects of the Invention]

Since the ion conductor of the present invention can increase the amount of the electrolyte solution impregnated regardless of the kind of the solvent of the electrolyte solution or the concentration of the supporting electrolyte, the ion conductivity is high and the leakage of the impregnated electrolyte is unlikely to occur.

1 is a schematic diagram of a display element using an ion conductor according to the present invention.

2 is a schematic diagram of a display element using an ion conductor according to the present invention.

Fig. 3 is a transmission electron micrograph of fine particles of an organic polymer (polyamide) containing ultrafine particles of silica.

Explanation of the sign

1 Ion conductor of the present invention (containing material discolored by electrochemical redox reaction)

2 Transparent Materials

3 transparent electrode

4 counter electrodes

5 sealant

6 facing equipment

7 Coloring layer discolored by electrochemical redox reaction

8 Ion Conductor of the Invention

Best Mode for Carrying Out the Invention

Hereinafter, the ion conductor of this invention is explained in full detail.

(Organic polymer fine particles and inorganic compound ultra fine particles)

The organic polymer fine particles used in the ion conductor of the present invention contain ultrafine particles of an inorganic compound having an average particle diameter of 500 nm or less.

For the purpose of improving the membrane strength, pressure resistance characteristics, and the like of an ion conductor, it has been described that an inorganic fine particle of micron order silica or alumina is added to an intrinsic polymer electrolyte or a polymer gel electrolyte.

However, the fine particles of the organic polymer used in the present invention are not simply obtained by a mixture of an organic polymer and an inorganic compound, and contain 20 to 80 mass% of ultrafine inorganic compounds having an average particle diameter of 500 nm or less. Unlike the case of containing particles of the inorganic compound of the micron order, the organic polymer containing the ultrafine inorganic compound of 500 nm or less can increase the specific surface area by the BET method by increasing the content.

In addition, the ultrafine inorganic compound used by this invention means the microparticles | fine-particles of a nano order of 500 nm or less.

The type of the organic polymer is not particularly limited as long as it can contain an inorganic compound at a high content in the ultrafine state, but has a polar group having affinity with inorganic compounds such as metal oxides, metal hydroxides, metal carbonates, and the like. Urethane and polyurea are preferred.

As the method for producing these organic polymer fine particles, an organic solution (A) containing at least one compound selected from the group consisting of dicarboxylic acid dihalide, dihaloformate and phosgene and an organic solvent,

Aqueous solution containing metal compound, diamine, and water of at least one alkali metal element and other metal elements (B)

The method obtained by interfacial polycondensation which arises by contact with is mentioned.

For example, polyamide is obtained by polycondensation of dicarboxylic acid dihalide and diamine, and polyurethane is obtained by polymerization of diamine and dihaloformates such as dichloroformate and diamine, and polyurea is phosgene and the like. It is obtained by polycondensation with diamine, and the structure is determined according to the kind of these monomers used for polycondensation.

As an inorganic compound, although the inorganic compound selected from the group which consists of a metal oxide, a metal hydroxide, and a metal carbonate at least 1 type is mentioned as a preferable aspect, metal oxide is preferable because it is easy to form ultrafine particles with an average particle diameter of 500 nm or less.

Examples of the metal oxides include silica (SiO ₂ ), aluminum oxide, tin oxide, zirconium oxide, zinc oxide, and manganese oxide. In view of the amount of the impregnable electrolyte and the size of the ion conductivity, silica and aluminum oxide are preferred.

According to the above production method, the inorganic compound may be contained in an amount of 20 to 80 mass% in an ultrafine particle state having an average particle diameter of 500 nm or less. Further, from the viewpoint that the ultrafine particles of the inorganic compound are hard to come off from the fine particles of the organic polymer and the electrolyte impregnation ability is high, the average particle diameter of the ultrafine particles of the inorganic compound is preferably 300 nm or less, more preferably 100 nm or less, most preferably It is 50 nm or less.

In view of the balance between the electrolyte solution impregnation ability as a function of the ion conductor and the film properties such as the workability as the separator, the bending resistance and the heat resistance, the content rate of the ultrafine particles of the inorganic compound is preferably 30 to 70% by mass of the organic polymer fine particles. .

When attempting to complex an inorganic compound with an organic polymer by using a mixing device such as an extruder, it is necessary to include the inorganic compound in the organic polymer fine particles at a high content of 20% by mass or more in an ultrafine particle state of 500 nm or less because of the inherent self-aggregation property of the inorganic compound. This is very difficult in the present situation. However, the production method may be any method as long as the fine particles of the organic polymer can contain 20 to 80% by mass of the inorganic compound in the state of ultrafine particles of 500 nm or less by improving the surface treatment of the inorganic compound, the dispersing agent, the dispersing agent and the like.

It is preferable that the shape of the said organic polymer microparticles | fine-particles is microparticles whose average particle diameter is 1-1000 micrometers. Moreover, the average short diameter of the microparticles | fine-particles of an organic polymer is 20 micrometers or less, and the shape whose average aspect ratio is 5-20 is preferable. It is particularly preferable that the organic polymer fine particles have a curved microfiber (pulp) shape. The average particle diameter here is a particle diameter calculated | required by the arithmetic mean of a short diameter and a long diameter of a particle. When the organic polymer is not in the particulate form, the ultrafine particles of the inorganic compound in the organic polymer cannot effectively contribute to the formation of the specific surface area or the impregnation of the electrolyte solution.

The ion conductor of the present invention can be impregnated in a state where it is difficult to leak a large amount of electrolyte, and an ion conductor impregnated with an electrolyte solution of 500 to 2000% by mass with respect to fine particles of an organic polymer containing ultrafine particles of an inorganic compound can be produced. .

(Electrolyte amount)

The electrolyte solution in this invention consists of a supporting electrolyte and the solvent which melt | dissolves this.

The solvent may be either aqueous or non-aqueous, and in addition to water, propylene carbonate, dimethyl carbonate, 2-ethoxy ethanol, 2-methoxy methanol, isopropyl alcohol, N-methyl pyrrolidone, and dimethyl acetate Polar organic solvents, such as amide, dimethyl formamide, acetonitrile, butyronitrile, glutaronitrile, dimethoxy ethane, (gamma) -butyrolactone, ethylene glycol, propylene glycol, can be illustrated. In addition, in the case of an aqueous system, in order to prevent solidification at 0 degrees C or less, and to use an ion conductor under low temperature conditions, the solvent which is compatible with water among the said non-aqueous solvents can be used interchangeably.

Examples of the supporting electrolyte include lithium salts such as lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium nitrate, lithium sulfate, lithium borate fluoride and lithium hexafluorophosphate; Halogenated alkali metals such as sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide and potassium iodide; Ammonium salts such as tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, ammonium boride, ammonium boride, tetraethyl ammonium boride, tetrabutyl ammonium perchlorate, tetraethyl ammonium perchlorate, tetra-n-butyl ammonium perchlorate, sulfuric acid, hydrochloric acid, perchloric acid Etc. can be illustrated.

The concentration of the supporting electrolyte may be appropriately set according to the use and the required performance of the ion conductor of the present invention, and is not particularly limited.

(Production method of ion conductor)

The ion conductor of the present invention comprises an organic solution (A) containing at least one compound selected from the group consisting of dicarboxylic acid dihalide, dihaloformate and phosgene and an organic solvent,

Aqueous solution containing metal compound, diamine, and water of at least one alkali metal element and other metal elements (B)

The organic polymer fine particle synthesis process of obtaining organic polymer microparticles | fine-particles by the interfacial polycondensation which arises by contact with the above, and the method of having an impregnation process which impregnates the said organic polymer microparticles with an electrolyte solution, and impregnates the organic polymer microparticles with electrolyte solution can be carried out. Can be.

(Organic Polymer Fine Particle Synthesis Process)

In the organic polymer fine particle synthesizing step suitably used in the present invention, the monomer in the organic solution (A) and the diamine in the aqueous solution (B) are rapidly polycondensed by stirring under normal temperature and normal pressure for about 10 seconds to several minutes. The polymer is obtained in high yield. At this time, the alkali metal in the metal compound such as alkali silicate acts as a remover of hydrogen halide generated during polycondensation of the monomer and the diamine, thereby promoting the formation of fine particles of the organic polymer. Simultaneously with this reaction, the alkali metal-containing metal compound is a silica (glass) when the alkali metal component is removed, and an inorganic compound having a metal element other than the alkali metal when other silica compounds are used. By inversion, it becomes insoluble in an organic solution or water and precipitates as a solid. At this time, the production of the organic polymer fine particles by the polycondensation of the monomer and the diamine and the precipitation of the ultrafine particles of the inorganic compound occur in parallel instead of only one of them. The ultrafine particles of the order can be formed.

Examples of the dicarboxylic acid dihalide in the organic solution (A) include acid halides of aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, and sebacic acid; Acid halides of aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid; Or the acid halide of aromatic dicarboxylic acid which substituted hydrogen of the aromatic ring, etc. are mentioned.

As the dihaloformate compound in the organic solution (A), for example, hydroxyl groups of aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol All chloroformatted by phosgenation treatment; All hydroxyl groups of dihydric phenols having two hydroxyl groups in one or two or more aromatic rings, such as resorcin (1,3-dihydroxy benzene) and hydroquinone (1,4-dihydroxy benzene), are all used for the phosgenation treatment. And chloroformatted.

Phosgene in the organic solution (A) includes phosgene, diphosgene, and triphosgen.

The monomers illustrated above can be used individually or in combination of 2 or more types.

In this invention, the kind of organic polymer can be changed by selecting the monomer in organic solution (A). Polyamide can be obtained when dicarboxylic acid dihalide is used as a monomer, polyurethane can be obtained when dihaloformate is used, and polyurea can be obtained by reaction with diamine in aqueous solution (B) when phosgene is used.

The organic solvent used in the organic solution (A) can be used without particular limitation as long as it does not react with the various monomers or diamines and dissolves the various monomers in the organic solution (A). Among them, incompatible with water include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane, halogenated hydrocarbons such as chloroform and methylene chloride, and alicyclic hydrocarbons such as cyclohexane. As compatible with water, examples thereof include ethers such as tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, alkyl acetates such as ethyl acetate and propyl acetate, and the like.

When water and an incompatible solvent are used as the organic solvent of the organic solution (A), the polycondensation reaction is an interfacial polycondensation that occurs only at the interface between the organic solution (A) and the aqueous solution (B) to form a fibrous (pulp) shape. An organic polymer is easy to be obtained. In particular, when an acid halide of an aliphatic dicarboxylic acid is used as the monomer in the organic solution (A) and an aliphatic diamine is used as the monomer in the aqueous solution (B), the molecular weight of the organic polymer obtained can be easily increased. Polymer fine particles are easy to obtain.

On the other hand, when a solvent compatible with water is used as the organic solvent of the organic solution (A), since polycondensation occurs in the state where the organic solvent and water are emulsified, powdery organic polymer fine particles are easily obtained. Even when any organic solvent is used, the obtained organic polymer fine particles are powder or fibrous, and the inorganic compound to be contained is in an ultrafine state, and thus the specific surface area is increased, so that the electrolyte solution can be easily, quickly and largely impregnated.

The diamine in the aqueous solution (B) can be used without particular limitation as long as it reacts with each monomer in the organic solution (A) to produce an organic polymer. Specifically, aliphatic diamines, such as 1, 3- diamino propane, 1, 4- diamino butane, 1, 6- diamino hexane, and 1, 8- diamino octane, m-phenylene diamine, p-phenylene Aromatic diamine, such as diamine, or the aromatic diamine derivative which substituted hydrogen of the aromatic ring, etc. are mentioned. You may use these individually or in combination of 2 or more types.

The monomer concentration in the organic solution (A) and the diamine concentration in the aqueous solution (B) are not particularly limited as long as the polycondensation reaction proceeds sufficiently, but the concentration range of 0.01 to 3 mol / L from the viewpoint of bringing each monomer into good contact with each other. In particular, 0.05-1 mol / L is preferable.

To alkali silicate in the aqueous solution (B) include those represented by the No. 1, No. 2, No. 3 and so on of the composition formula of A ₂ O · nSiO ₂ water glass according to JIS K 1408. Here, A is an alkali metal and the average value of n is 1.8-4. Alkali metal compounds contained in the alkali silicate act as a remover of the acid generated when the monomer in the organic solution (A) and the diamine in the aqueous solution (B) polycondense, whereby the silicate alkali promotes the polycondensation of the monomer and the diamine. At the same time, by converting into silicon oxide (silica) which is insoluble in a polar solvent, a raw material of ultrafine particles of the inorganic compound contained in the fine particles of the organic polymer can also be used.

, Of a metal compound with the alkali metal element and other metal elements in at least one kind of the aqueous solution (B) it may be a compound that can be represented by the general formula A _x M _y B _z. Here, A is an alkali metal element, M is a transition metal element of group 3 to 12 of the periodic table or a typical metal element of group 13 to 16 of the periodic table, and B is at least selected from the group consisting of O, CO ₃ , OH It is 1 type, and x, y, z are numbers which allow the coupling | bonding of A, M, and B. It is preferable that the compound represented by the general formula A _x M _y B _z is dissolved in water to show basicity. Alkali metals contained in the alkali metal-containing metal compounds also act as a remover of the acid generated during polycondensation, in the same way as alkali metal compounds in alkali silicates, thereby promoting polycondensation between monomers and diamines and insoluble in polar solvents. By converting into a phosphorus metal compound, it becomes a raw material of ultrafine particles of an inorganic compound contained in an organic polymer.

Among the alkali metal-containing metal compounds, compounds in which B in the general formula is O (oxygen atom) include sodium zincate, sodium aluminate, sodium chromate, sodium molybdate, sodium stannate, sodium titanate, sodium vanadate, and tungsten Sodium complex oxides such as sodium acid; Potassium complex oxides such as potassium zincate, potassium aluminate, potassium chromate, potassium molybdate, potassium stannate, potassium manganate, potassium tantalate, potassium tungstate, potassium stannate, potassium nitrate and the like; In addition to lithium complex oxides, such as lithium aluminate, lithium molybdate, and lithium stannate, a rubidium complex oxide, a cesium complex oxide, etc. are mentioned.

Examples of the alkali metal-containing metal compound in which B in the general formula includes both groups of CO ₃ and OH include zinc carbonate, nickel carbonate, potassium zirconium carbonate, cobalt carbonate, tin carbonate, and the like.

Since these alkali metal containing metal compounds are dissolved and used in water, they may be a hydrate. In addition, these can be used individually or in combination of 2 or more types. Moreover, you may use simultaneously with the said silicate alkali.

The inorganic compound is preferably a metal oxide, and examples of the metal oxide include aluminum oxide, tin oxide, zirconium oxide, zinc oxide, manganese oxide, molybdenum oxide, tungsten oxide and silica. Among these, aluminum oxide and silica are preferable because the average particle diameter of the fine particles is small and the microdispersibility is good.

On the other hand, as the organic polymer, polyamide, polyurethane and polyurea are preferable. The particulate shape of the organic polymer and the ultrafine particle shape of the inorganic compound depend on the combination with the organic polymer. In this combination, microparticles | fine-particles of the organic polymer in which the ultrafine particle | grains of aluminum oxide and / or silica are contained in the organic polymer microparticles of polyamide are mentioned as a preferable aspect.

(Production apparatus for organic polymer fine particles)

The manufacturing apparatus used for synthesizing the organic polymer fine particles by the above production method is not particularly limited as long as it is a device capable of bringing the organic solution (A) and the aqueous solution (B) into good contact, and is a continuous or batch type. ) Can be any way. When aliphatic diamine is used as the diamine in the aqueous solution (B) and aliphatic dicarboxylic acid dihalide is used as the monomer in the organic solution (A), a solid gel-like substance may be produced by polycondensation. In this case, it is preferable to use a mixer having a high shear force because the gel is crushed to advance the reaction, and examples of the mixer include a blender manufactured by OSTERIZER.

The polycondensation reaction between the monomer in the organic solution (A) and the diamine in the aqueous solution (B) proceeds sufficiently in the temperature range around normal temperature of, for example, -10 to 50 ° C. Therefore, the temperature at which the organic solution (A) and the aqueous solution (B) are brought into contact with each other is set at a temperature in the vicinity of room temperature of -10 to 50 ° C. At this time, pressurization and pressure reduction are not required. In addition, although polycondensation reaction is based also on the monomer type and the reactor used, it is usually completed in a short time of 15 minutes or less.

(Production process of ion conductor)

The ion conductor of this invention can be obtained by impregnating electrolyte solution to the microparticles | fine-particles of the organic polymer obtained in this way. Although the organic polymer microparticles | fine-particles obtained by the said organic polymer microparticles | fine-particles synthesis process are obtained in the wet cake state which impregnated 400-700 mass% water with respect to the organic polymer microparticles | fine-particles, the organic polymer microparticles | fine-particles of a wet cake state impregnated electrolyte solution. The water may be replaced with an electrolyte solution, and the organic polymer fine particles in the wet cake state may be dried once, and the organic polymer fine particles in the dry state may be impregnated with the electrolyte solution. However, when the organic polymer microparticles in the wet cake state are dried, the organic polymer microparticles solidify firmly by hydrogen bonding derived from the polar group of the organic polymer, and the organic polymer microparticles hardly absorb the electrolyte solution, and the amount of the electrolyte solution impregnation is reduced. Since it cannot become much, the method of impregnating electrolyte solution to the organic polymer microparticles | fine-particles of a wet cake state, and replacing a polar solvent with electrolyte solution is preferable.

As a method of impregnating an electrolyte solution to the microparticles of an organic polymer, the method of making organic polymer microparticles | fine-particles in a previously prepared electrolyte solution, fully disperse | distributing, and filtering, the method of impregnating electrolyte solution by circulating an electrolyte solution to organic polymer microparticles, and an organic polymer Although the method of distilling off the polar solvent originally contained after disperse | distributing microparticles | fine-particles in electrolyte solution is mentioned, It is not limited to these. Since the organic polymer fine particles in the present invention have very high electrolyte solution impregnation characteristics by the estimation mechanism described later, the organic polymer fine particles are simply subjected to a simple operation of injecting and dispersing the organic polymer fine particles in the electrolyte solution and performing filtration. It can be set as the wet cake which impregnated 500-2000 mass% electrolyte solution with respect to microparticles | fine-particles. Moreover, since the said organic polymer microparticles | fine-particles are obtained in fibrous form or powder, dispersion of organic polymer microparticles | fine-particles in electrolyte solution can also be easily performed using a general-purpose batch type stirring layer.

(Processing Characteristics of Ion Conductor)

When the organic polymer fine particles have a fibrous shape, particularly preferably a fiber diameter of 20 μm or less and a pulp shape with an aspect ratio of 10 or more, it has papermaking properties, and in the case of powder, it has coating properties. The organic polymer fine particles themselves have the processability and are easy to handle. In particular, in the case where the organic polymer fine particles are fibrous, a wet cake having high tensile strength, flexibility, or high yieldability against bending may be obtained by filtering the liquid in which the electrolyte is dispersed in the organic polymer fine particles. You can get it. Therefore, even if the ion conductor which consists only of organic polymer microparticles | fine-particles and electrolyte solution is used, without having to complex or mix another material, it can serve as a separator.

(Immersion Mechanism of Electrolyte for Expression of Ionic Conductivity)

Since the ion conductor of the present invention can be impregnated with a large amount of an electrolyte solution of 500 to 2000% by mass with respect to the organic polymer fine particles, the ion conductor can have almost the same ion conductivity as the electrolyte solution in which the supporting electrolyte is dissolved. The electrolyte solution impregnation characteristic in the ion conductor of the present invention is considered to be expressed by the chemical properties and geometrical factors of the ultrafine particles of the organic polymer of the organic polymer fine particles and the inorganic compound contained in the organic polymer.

The inorganic compound in organic polymer microparticles | fine-particles has high affinity with a polar solvent, as represented by a silica, a metal oxide, a metal hydroxide, a metal carbonate, etc. Moreover, the content rate of an inorganic compound is 20-80 mass% high, and an inorganic compound is ultrafine particle with an average particle diameter of 500 nm or less.

In addition, since the organic polymer also has a particulate form, ultrafine particles of the inorganic compound are likely to be present on the surface of the organic polymer fine particles, not inside the organic polymer. Since the fine particles of the inorganic compound of nanometer order having a very large surface area per unit mass exist on the surface of the fine particles of the organic polymer, a stronger affinity to the polar solvent is provided by the wider surface. In addition, it is considered that the voids are formed by the inorganic particles of the ultrafine particles existing on the surface among the organic polymer fine particles, so that the organic polymer fine particles exhibit the impregnation characteristics of a large amount of electrolyte solution.

As described above, since the ion conductor of the present invention can impregnate most of the polar solvent including water, there is no limitation on the kind of the polar solvent of the electrolyte solution. Further, even if the concentration of the supporting electrolyte in the electrolyte is increased, the electrolyte impregnation characteristic is hardly affected.

In order to increase the specific surface area to increase the impregnation amount of the electrolyte, the average particle diameter of the ultrafine particles of the inorganic compound is preferably 300 nm or less, more preferably 100 nm or less. Moreover, 40 mass% or more is preferable, as for the content rate in the ultrafine particle of the ultrafine particle of an inorganic compound, 60 mass% or more is more preferable, and the polymer fine particle of this invention can contain 80 mass%.

(Specific surface area)

The BET multi-point method (multi-point method) a specific surface area of 30m ² / g~150m ² / g as measured as the content of the ultrafine particles of the inorganic fine particles containing the polymer of the organic compound increases from 20 mass% to 80 mass% To increase is to support the impregnation mechanism.

In particular, when the inorganic compound is silica or aluminum oxide, the ultrafine particles of the inorganic compound have a very small particle diameter of about 10 nanometers, and form a network structure in which the fine particles of the inorganic compound are partially connected to each other. ) Revealed by observation. By this structure, the organic polymer fine particles have a high specific surface area of 50 to 150 m ² / g, and can have higher electrolyte solution impregnation.

When the organic polymers are polyamides, polyurethanes, and polyurea, the amide bonds, urethane bonds, and urea bonds possessed by the polymers have an affinity for containing fine particles of inorganic compounds and polar solvents, so that more electrolytes can be impregnated. Is preferred.

In this way, the organic polymer component also contributes to the electrolyte solution impregnation characteristics, but many electrolyte solutions cannot be impregnated only by the affinity of the organic polymer. When the organic polymer (polyamide) fine particles containing no inorganic compound are synthesized by using caustic soda instead of the metal compound having alkali metal in the above-described organic polymer fine particle synthesis process, the fine particles of the organic polymer have a fibrous shape. Nevertheless, only the BET specific surface area of less than 1 m ² / g was shown, and the amount of the electrolyte impregnation was also very low. From this, the combination of the organic polymer in the particulate state and the inorganic compound in the ultrafine state contained in the ion conductor of the present invention is important, and the organic polymer having a BET specific surface area of 30 m ² / g or more satisfies the object of the present invention. It provides an ion conductor to make.

The ion conductivity of the ion conductor of the present invention varies greatly depending on the amount of the electrolyte solution impregnated with the organic polymer and its ion conductivity, but more than 1 × 10 ⁻³ S / cm can be achieved, more preferably 2 × 10 ⁻³ S / cm or more, more preferably 5 × 10 ⁻³ S / cm or more can be achieved.

(Mechanical and thermal characteristics)

Conventional ion conductors such as polymer gel electrolytes are not sufficiently compatible with high ionic conductivity and membrane properties such as bending resistance and heat resistance for preventing short circuit as a separator.

The fine particles of the organic polymer used in the present invention can have high heat resistance because the fine particles of the inorganic compound have a reinforcing effect on the organic polymer (for example, the organic polymer is polyamide, the inorganic compound is silica, and silica The microparticles | fine-particles of the organic polymer whose content rate of is 60 mass% do not change a physical property to 300 degreeC). The ion conductor of this invention which impregnated this with a polar solvent is also excellent in heat resistance.

(Solvent resistance, repeated durability)

In addition, the microparticles | fine-particles of the organic polymer in this invention can have high solvent resistance. For example, when microparticles of an organic polymer in which an organic polymer is polyamide and an inorganic compound is silica are used, they are very stable to liquids other than cresols in which polyamide is dissolved and strong alkali solution in which silica is dissolved. For this reason, even a strong acid solution in which hydrochloric acid, sulfuric acid or nitric acid is dissolved can be used as the electrolyte solution. In addition, when the ion conductor of the present invention is used as a member of an electrochemical device such as a secondary battery, an electric double layer capacitor, or an electrochemical display device, deterioration of the organic polymer fine particles even after repeated charging and discharging or discoloration is performed. There is almost no.

One of the features of the present invention is that the ion conductor of the present invention can be used alone, but for the purpose of improving the strength at the time of film formation of the ion conductor, all binders such as binders and various resins are required. You may contain in the range which does not impair a characteristic.

(Electronic insulation)

The ion conductor of the present invention can be used as a separator for an electrolyte or an electric double layer capacitor of a battery. In this case, since the ion conductor needs to have electron insulating property, it is preferable not to use a material having electron conductivity for the organic polymer and the inorganic compound constituting the organic polymer fine particles.

As an inorganic compound, when using tin oxide etc. which have electron conductivity, and having high content of about 60 mass% or more, it may have electron conductivity. However, raw materials for inorganic compounds other than these have little electron conductivity and can be used without problems. Since the organic polymer does not have electronic conductivity in any of polyamide, polyurethane, and polyurea, it can be suitably used as a separator for electrolytes or electric double layer capacitors in batteries.

(Medium for Electrochemical Display Devices)

The ion conductor of the present invention can be suitably used as a medium for electrochemical display devices. The ion conductor of the present invention can be used as a medium for an electrochemical display device as a material excellent in ion conductivity, electron insulation, bending resistance, and heat resistance. It is possible to fabricate a display device having excellent color development due to electrochemical reactions such as contrast and response speed. In particular, the reflective display element medium in which the ion conductor exhibits white color by reflection of an external light source is easily fatigued for the reason that the directional vertical light, which the display surface follows with the brightness of the surroundings, does not enter the eye. The biggest advantage is that it can endure long time use without being damaged. In order to fully realize these advantages, it is important to know how to produce a natural, soft, paper-like white color by light scattering.

The ion conductor of the present invention is a white medium having a paper texture, and can be used as a medium for a so-called paper white display element. For example, Japanese Patent Application Laid-Open No. 14-258327 discloses an electrochromic display device having a polymer solid electrolyte layer containing a white colorant such as titanium oxide and a polymer material layer discolored by electrochemical redox, and a white colorant. As an example, an electrodeposition type display device comprising a polymer solid electrolyte layer containing a metal ion as a colorant as a titanium oxide or the like is sandwiched between electrodes. However, since this method uses a white pigment, visibility and texture are significantly different from paper. In addition, a large amount of white pigment must be added to obtain sufficient white color. On the other hand, when 20 mass% or more of white pigments are contained, aggregation occurs, and the white pigments do not participate in ion conduction, and the ion conductance worsens. Therefore, there is a problem that the response speed of the display is delayed and the driving voltage is increased.

The ion conductor of the present invention can be used as a display medium having high whiteness and close visibility to paper by using fibrous organic polymer fine particles, thereby providing a reflective electrochemical display device having visibility and texture very close to paper. can do.

(White-colored mechanism by organic polymer component species)

When used as a medium for display elements, the organic polymer of the ion conductor is preferably polyamide, polyurethane and polyurea. In addition, when the whiteness is high, since the visibility can be improved by increasing the contrast at the time of color development, it is preferable not to have a conjugated system in the polymer chain. Therefore, aliphatic polyamides, polyurethanes and polyureas are preferably used.

Among these, organic polymer fine particles having a fiber diameter having a short diameter of 20 μm or less and having an aspect ratio of 10 or more are dispersed and filtered in an electrolyte solution, whereby a sheet-shaped ion conductor having a large impregnation capacity of the electrolyte solution is obtained with almost the same appearance as paper. . Since the ion conductor has random minute irregularities or voids on the surface or inside, the incident light is scattered in each direction at the interface between the impregnated electrolyte and the polymer particles. Since it is a white color mechanism similar to paper, it can produce white close to paper, and therefore it is particularly preferably used. At this time, the electrolytic solution impregnated with the fine particles of the organic polymer has a colorant which is discolored by an electrochemical redox reaction, so that the colorant can be displayed on a background similar to paper. In particular, by using a colorant which is reversibly discolored by an electrochemical redox reaction, the ion conductor of the present invention can be suitably used as a medium for an electrochemical display device.

(White color mechanism by inorganic species)

The ultrafine particles of the inorganic compound contained in the organic polymer fine particles are preferably used because a material exhibiting colorless or white color can increase the whiteness of the display medium. Such materials include silica, aluminum oxide, zirconium oxide, zinc oxide, tin oxide and the like.

Since zirconium oxide, zinc oxide, and tin oxide can be made into ultrafine particles having an average particle diameter of 100 nm to 500 nm in the ion conductor of the present invention, they contribute to electrolyte impregnation and have a high refractive index of 2 or more. The light scattering can be satisfactorily generated between the electrolyte solution and the high whiteness can be imparted.

On the other hand, the organic polymer fine particles in which the inorganic compound obtained by the above-described organic polymer fine particle synthesis process is silica and aluminum oxide have a very small particle diameter of about 10 nm, and ultrafine particles of the inorganic compound can form a network structure. It was revealed by transmission electron microscopy (TEM) observation. At this time, when the size of the entire network composed of the ultrafine particles of the inorganic compound is larger than the wavelength of the visible light, scattering of the visible light occurs at high efficiency at a very wide interface of the organic polymer fine particles, thereby providing very high whiteness to the organic polymer fine particles. Because it is used particularly preferably.

(Electrolyte for display media)

In the electrolytic solution used in the ion conductor of the present invention, a coloring agent discolored by an electrochemical redox reaction can be added and used as a medium for a display device. The coloring agent may be an organic compound or a metal compound.

Organic Compound Coloring Agent

Organic compounds used as colorants include quinone compounds and leuco dyes. As the quinone compound, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, tert-butylanthraquinone (above red), dihydroxyanthraquinone, 1,5-dichloroanthraquinone (above violet), 2- Sulfonic acid anthraquinone (yellow), benzanthraquinone (green), etc., and organic quinones which are derivatives thereof can be illustrated. These organic quinones produce a coloring state peculiar to each compound by applying a driving voltage to the electrodes. Moreover, as a leuco dye, blue, such as black leuco dyes, such as 2-amino-6-diethylamino-3-methylfluoran, 3, 3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, etc. 3-cyclohexylamino-6-chlorofluorane (orange), 3-diethylamino-7,8-benzofluoran (pink), in addition to red leuco dyes such as leuco dye, 9-diethylaminobenzofluoran, 2-anilino-6-diethylaminofluorane (green) can be illustrated.

(Metal Compound Coloring Agent)

When metal ion is reduced in electrolyte solution, it is known to precipitate and color on an electrode. Examples of such metal ions include ions such as silver, bismuth, copper, iron, chromium and nickel, which are ionized by dissolving halides, sulfides, sulfates, nitrates and perhalogenates of these metals in an electrolyte solution, The electrolyte solution can be used as a color developer. For example, when using an electrolyte solution obtained by dissolving the compound, by applying a driving voltage to the electrode Ag ^{+ +} e ^- → Ag on the reduction reaction taking place cathode side, and a change in black above the electrode by the Ag precipitates. Since bismuth and silver in the said metal are almost transparent in the state which melt | dissolved in electrolyte solution, since the color of precipitate is dark and the reversible reaction of a small coloration is favorable, it is especially used preferably. In addition, you may use these metal ions in combination of 2 or more type.

Among the metal compounds used as metal ion sources, silver compounds include silver halides such as silver chloride, silver bromide, and silver iodide. May be exemplified. Examples of the bismuth compounds include bismuth oxide, bismuth hydroxide, bismuth oxychloride, bismuth oxy perchlorate, bismuth oxy sulfate, bismuth sulfate, bismuth sulfide, bismuth nitrate, bismuth phosphate, and the like, in addition to bismuth chloride such as bismuth chloride and bismuth bromide. have.

When using the above-mentioned small color development compound, it is necessary to select the solvent suitable for each coloring agent, or a support electrolyte as a suitable material. In the ion conductor of the present invention, the refractive index of the organic polymer is usually about 1.5, but by using an electrolyte solution having a large difference from the refractive index, the whiteness derived from light scattering is higher, and thus a display medium having visibility and texture close to paper can be obtained. . Therefore, the solvent of refractive index of 1.40 or less preferably, More preferably, the solvent of 1.38 or less is used. Examples of such solvents include nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, 2-ethoxy ethanol, 2-methoxy methanol and isopropyl alcohol, ethyl acetate and isopropyl acetate. Alkyl acetates and these mixtures can be illustrated.

Moreover, in order to improve the reversibility of small color development, you may use various additives, such as a redox promoter, a buffer, a pH adjuster, and a brightening agent.

The manufacturing method of the medium for display elements of this invention should just dissolve the organic or inorganic coloring agent in the electrolyte solution used previously at the electrolyte solution impregnation process of preparation of an ion conductor. Other than that is the same as that of embodiment of preparation of an ion conductor.

(Display element)

An electrochemical display device can be fabricated from two electrode plates, an ion conductor of the present invention held between the two electrode plates, and a material reversibly discolored by an electrochemical redox reaction caused by ion conduction in the ion conductor. Can be.

There are two types of display elements using the ion conductor of the present invention.

The first type of electrochemical display device is an electrochemical display device having a structure in which a material reversibly discolored by an electrochemical redox reaction is contained in an ion conductor.

The structure of this electrochemical display element is shown in FIG. When the upper side of FIG. 1 is viewed, 1 is an ion conductor (using a colorant-containing electrolyte solution) of the present invention, 2 is a transparent substrate such as glass or plastic, 3 is a transparent electrode such as ITO, 4 is a counter electrode, and 5 is a Sealing agent 6 is an opposing base material.

The second type electrochemical display device is the above electrochemical display device in which a material which is reversibly discolored by an electrochemical redox reaction forms a color layer provided on an electrode plate.

In this case, the electrolyte solution impregnated with the ion conductor does not need to contain a coloring agent discolored by electrochemical redox. The structure of this electrochemical display element is shown in FIG. 2 is a transparent substrate such as glass or plastic, 3 is a transparent electrode such as ITO, 4 is a counter electrode, 5 is a sealant, 6 is a counter substrate, and 7 is an electrochemical redox. The coloring layer discolored by 8 is an ion conductor of the present invention (using an electrolyte solution containing no coloring agent).

(electrode)

It is necessary for the electrode plate used in the present invention to be located on the viewing side. These include ATO (antimony tin oxide), TO (tin oxide), ZO (zinc oxide), IZO (indium zinc oxide), FTO (fluorine-doped tin oxide), etc. The thing formed on the board | substrate can be illustrated. On the other hand, the electrode plate facing the transparent electrode does not necessarily need to be transparent, and therefore, in addition to the metal oxide, electrochemically stable metals such as platinum, gold, silver, copper, bismuth, cobalt, palladium, and the like or carbon material Can also be used.

(materials)

The substrate used in the present invention is not particularly limited as long as the surface is smooth, the light transmittance is high, and the electrode can be provided. Specifically, plastic sheets, such as polyethylene terephthalate, polyester, polycarbonate, a glass plate, etc. are mentioned. In the case of the substrate used on the opposite side of the viewing face, the light transmittance does not need to be high.

(Sealing agent)

The sealant 5 is provided to maintain the gap between the electrodes and to prevent the incorporation of moisture, oxygen or carbon dioxide in the air into the medium 1 for the electrochemical display device. And pressure-curable curing by ultraviolet rays, and resins having gas barrier properties.

(Chromic layer discolored by electrochemical oxidation or reduction)

In the present invention, as shown in Figure 2, it is possible to provide a display device provided with a color layer which is discolored by the electrochemical oxidation or reduction reaction in contact with the electrode. An organic compound and a metal compound can be used as such a coloring layer. Examples of the organic compound constituting the chromophoric layer include high molecular compounds such as polypyrrole, polyaniline, polyazulene, polythiophene, polyindole and polycarbazole. In particular, polypyrrole has a dark colored precipitate and a reversible color reaction. Since it is favorable, it is used preferably. In addition, examples of the inorganic compound constituting the coloring layer include WO ₃ , MoO ₃ , V ₂ O ₅ , Nb ₂ O ₅ , TiO ₂ , NiO, Cr ₂ O ₃ , MnO ₂ , CoO, IrO ₂ , and the like. . In this system, it is necessary to form the coloring layer in which these quenching color arises on one transparent electrode of the said board | substrate. In the case of using an organic compound as the color developing layer, the layer can be formed on the transparent electrode by electropolymerization or chemical polymerization of the raw material monomer of the polymer compound. When using a metal compound, it can form into a film by well-known methods, such as the vacuum deposition method, the electron beam vacuum deposition method, and the sputtering method.

In addition, by applying a coloring agent-containing coating solution or a gel-like substance mixed with various binder resins together with the supporting electrolyte or solvent to the organic or inorganic coloring material illustrated in the first method, the same as in FIG. A display element can be manufactured. In this case, a coloring layer can be provided by a coating method, a spin coating method, or the like.

(Electrochemical device)

In the present invention, an electrochemical display device can be obtained by forming a power supply portion, a circuit portion, or a sealing layer, a housing, or the like, in the display element shown in FIG. 1 or 2.

In addition, the use of the ion conductor of the present invention is not limited to the display element, and can be suitably used as a member of an electrochemical device such as a secondary battery, an electric double layer capacitor, a solar cell, and the like.

Hereinafter, the present invention will be described in more detail using examples. Unless otherwise specified, "parts" means "parts by mass".

Synthesis Example 1 Synthesis of Organic Polymer Fine Particles; Organic Polymer: Polyamide, Inorganic Compound: Silica

1.58 parts of 1,6-diaminohexane and 9.18 parts of water glass No. 3 were added to 81.1 parts of ion-exchanged water, and it stirred at 25 degreeC for 15 minutes, and obtained the homogeneous transparent aqueous solution (B). This aqueous solution (B) was put into the blender bottle made from Osterizer company at room temperature, and the organic solution (A) which melt | dissolved 2.49 parts of adipoyl chlorides in 44.4 parts of toluene was dripped over 20 second, stirring at 10000 rotations every minute. The resulting gelled material was broken with a spatula and stirred for 40 seconds at 10000 revolutions per minute. The liquid in which the fibrous product obtained by this operation was dispersed was filtered under reduced pressure on a filter paper having a pore size of 4 µm using a nutche of 90 mm in diameter. The product on the lacquer was dispersed in 100 parts of methanol, and washed with stirring under reduced pressure for 30 minutes. Subsequently, the same washing operation was carried out using 100 parts of distilled water and filtered under reduced pressure to obtain a wet cake (wet cake (1)) containing water of pure white organic polymer fine particles (silica / polyamide).

Synthesis Example 2 Synthesis of Organic Polymer Fine Particles; Organic Polymer: Polyamide, Inorganic Compound: Aluminum Oxide

Aqueous solution of (B) a put in ion-exchanged water 81.1 parts 1,6-diaminohexane 1.58 parts of sodium aluminate _{(Na 2 O / A1 2 O} 3 molar ratio = 1.13), 2.26 parts of the resulting homogeneous transparent and stirred for 15 minutes at room temperature A wet cake (wet cake (2)) containing water of pure white organic polymer fine particles (aluminum oxide / polyamide) was obtained in the same manner as in the method described in Synthesis Example 1 except that the aqueous solution (B) was used.

Synthesis Example 3 Synthesis of Organic Polymer Fine Particles; Organic Polymer: Polyamide, Inorganic Compound: Zirconium Oxide

A homogeneous aqueous solution obtained by adding 1,6-diaminohexane 1.58 parts and 1.79 parts of potassium zirconium carbonate (K ₂ [Zr (OH) ₂ (CO ₃ ) ₂ )) to 38.5 parts of ion-exchanged water as an aqueous solution (B). A wet cake (wet cake (3)) containing water of pure white organic polymer fine particles (zirconium oxide / polyamide) was obtained in the same manner as in the method described in Synthesis Example 1 except that (B) was used.

Synthesis Example 4 Synthesis of Polyamide without Inorganic Compound

Wet cake containing water of pale yellow polyamide containing no ultrafine particles of an inorganic compound in the same manner as described in Synthesis Example 1, except that 1.18 parts of sodium hydroxide was used instead of water glass 3 as the aqueous solution (B). (Wake cake (4)) was obtained.

The obtained various organic polymer fine particles were analyzed in accordance with the following method.

(Measurement method of inorganic compound content (ash))

After drying the wet cake of each organic polymer microparticles completely, it weighs correctly (mass of organic polymer microparticles | fine-particles), and calcinates this at 600 degreeC in air for 3 hours, burns away an organic polymer component completely, and removes the mass after baking It measured and it was set as the ash mass (= inorganic compound mass). The inorganic compound content rate was computed by the following formula.

Inorganic compound content (mass%) = (mass of ash / mass of organic polymer fine particles) x 100

(Measurement of particle size and observation of dispersed state of ultrafine particles of inorganic compound in organic polymer fine particles)

The organic polymer microparticles | fine-particles were heat-pressed at 170 degreeC and the conditions of 20 MPa / cm <^2> for 2 hours, and the flakes of the organic polymer microparticles of about 1 mm in thickness were obtained. This was made into an ultrathin slice having a thickness of 75 nm using a microtome. The obtained section was observed with a transmission electron microscope "JEM-200CX" manufactured by JEOL Ltd. (JEOL Ltd.). It was observed that the inorganic compound was a dark phase and was finely dispersed in a bright organic polymer. 3 is a transmission electron microscope photograph of organic polymer fine particles (silica / polyamide).

Subsequently, the short and long diameters of 100 inorganic compound particles were measured using a transmission electron microscope photograph, and the arithmetic mean value was made into the average particle diameter of an inorganic compound. In this observation, it was observed that in the organic polymer fine particles (silica / polyamide), silica, which is estimated to be about 10 nm spherical, was network-shaped, that is, three-dimensionally networked and undispersed in the polyamide. In the organic polymer fine particles (aluminum oxide / polyamide), it was observed that about 10 nm of aluminum oxide, which is assumed to have a plate shape, was undispersed in the fine particles of polyamide by forming a network in layers, that is, two-dimensionally. . On the other hand, in organic polymer microparticles | fine-particles (zirconium oxide / polyamide), it was observed that each particle | grain of about 150 nm zirconium oxide particle is disperse | distributed independently.

Preparation of Electrolyte with Coloring Agent and Supporting Electrolyte

According to the following method, the aqueous electrolyte solution and the organic electrolyte solution were manufactured.

Preparation Example 1 Aqueous Electrolyte (Coloring Agent: Bismuth)

An electrolytic solution (1) consisting of 20.0 g of water as a solvent, 0.54 g of bismuth oxy perchlorate as a colorant, 0.42 g of a 60% by mass solution of perchloric acid as a supporting electrolyte, and 0.28 g of hydroquinone as a reducing accelerator were prepared. Each electrolyte was completely dissolved in water, and the electrolyte solution was transparent and uniform. The refractive index of water is 1.33 at room temperature.

Preparation Example 2 Organic Electrolyte (Coloring Agent: Silver)

An electrolyte solution (2) consisting of 20.0 g of acetonitrile as a solvent, 0.71 g of silver bromide as a color developer and 2.30 g of lithium bromide as a supporting electrolyte was prepared. This electrolyte solution was completely transparent by dissolving each component in acetonitrile. The refractive index of acetonitrile is 1.34 at room temperature.

(Example 1)

About 10 g of the wet cake (1) obtained in Synthesis Example 1 was dispersed in 100 g of ultrapure water, and the process of filtration under reduced pressure was repeated three times to give a washing process to obtain about 10 g of a wet cake having ultrapure water. After mass measurement of the obtained wet cake (wet mass), it dried at 150 degreeC for 2 hours, and measured the mass (dry mass). From these numerical values, the solid content fraction of the wet cake 1 was calculated by the following equation.

Solid fraction (mass%) = (dry mass / wet mass) × 100

From this solid fraction, the wet cake calculated so that the sample solid content was 0.3 g was dispersed in the aqueous electrolytic solution 1 prepared in Preparation Example 1 at room temperature for 10 minutes, and then dispersed, and then mixed on a 4 μm filter paper for 5 minutes. By filtration under reduced pressure at 0.02 MPa, the ion conductor la of the present invention having a thickness of about 700 μm with an aqueous electrolyte solution was prepared.

(Example 2)

The ion conductor 2a of this invention was produced by the method similar to Example 1 except having used the wet cake 2 obtained by the synthesis example 2 instead of the wet cake 1 in Example 1.

(Example 3)

The ion conductor 3a of the present invention was produced in the same manner as in Example 1 except that the wet cake 3 obtained in Synthesis Example 3 was used instead of the wet cake 1 in Example 1.

(Comparative Example 1)

An ion conductor 4a containing no ultrafine particles of an inorganic compound was produced in the same manner as in Example 1 except that the wet cake 4 obtained in Synthesis Example 4 was used instead of the wet cake 1 in Example 1. did.

(Example 4)

Ultrapure water washing of the wet cake 1 was carried out in the same manner as in Example 1, and then each obtained wet cake was dispersed in 100 g of acetonitrile, and the process of performing filtration under reduced pressure was repeated three times, whereby the liquid component was almost acetonitrile. About 10 g was obtained. An ion of the present invention having a thickness of about 700 μm having an organic electrolyte solution from the wet cake by the same method as in Example 1, except that the electrolyte solution 2 containing acetonitrile prepared in Preparation Example 2 as a solvent was used instead of the aqueous electrolyte solution. The conductor 1b was produced.

(Example 5)

An ion conductor (2b) of the present invention was produced in the same manner as in Example 4 except that the wet cake (2) obtained in Synthesis Example 2 was used instead of the wet cake (1) in Example 4.

(Example 6)

The ion conductor 3b of this invention was produced by the method similar to Example 4 except having used the wet cake 3 obtained by the synthesis example 3 instead of the wet cake 1 in Example 4.

(Comparative Example 2)

An ion conductor 4b containing no fine particles of an inorganic compound was produced in the same manner as in Example 4 except that the wet cake 4 obtained in Synthesis Example 4 was used instead of the wet cake 1 in Example 4. did.

After the mass measurement of the ion conductors (1a) to (4a) (cake mass), 15 times of ultrapure water of the cake mass was added, and the support electrolyte and the like were completely removed by repeating the dispersion washing and the filtration under reduced pressure three times at room temperature for 30 minutes. , Wet cake with only ultrapure water was obtained. This wet cake was dried under reduced pressure at 150 degreeC for 2 hours, and the mass was measured (dry mass). From these numerical values, the impregnation rate (electrolyte solution impregnation amount) of the electrolyte solution with respect to the organic polymer fine particles was calculated by the following equation. Similarly, after the same washing treatment was performed with acetonitrile on the ion conductors 1b to 4b, the impregnation rate of the electrolyte solution with respect to the organic polymer fine particles was calculated.

Electrolytic solution impregnation rate (mass%) = {(cake mass-dry mass) / dry mass} × 100

The ion conductivity at 25 degrees C of each ion conductor was measured by the alternating current impedance method using the Toyo Technica Impedance Analyzer type 1260 and the sample holder for liquid measurement.

The ion conductor was mounted on a standard black plate, and the reflectance (%) (based on the standard white plate) in the vertical direction of the ion conductor under the diffused light source was measured using the display evaluation system DMS-5000 (manufactured by Otronic).

Table 1 shows the physical properties of the organic polymer fine particles with respect to the organic polymer fine particles obtained in Synthesis Examples 1 to 4. Table 1 also shows the specific surface area of the organic polymer fine particles measured by the following method.

(Measurement of specific surface area)

Approximately 0.2 g of the dried sample obtained by completely drying each obtained wet cake by drying at 170 ° C. for 2 hours in a hot air dryer is set on a fully automatic gas adsorption apparatus Auto Soap 1C manufactured by Yuasa Ionics Co., Ltd. according to the specific surface area measurement method of JIS Z8830. Using the nitrogen gas as the adsorption gas, the gas adsorption amount was measured at five points in the range of 0.05 to 0.3 relative pressure (P / P ₀ ), and the specific surface area (m ² / g) of each sample was determined by the BET multipoint method. ) Was measured.

TABLE 1

Synthesis Example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Wet Cake (1) Wet Cake (2) Wake Cake (3) Wet Cake (4) Contains inorganic ingredients SiO ₂ Al ₂ O ₃ ZrO ₂ - Mineral content (mass%) 60 40 45 0 Inorganic particle diameter (nm) 10 10 150 - Specific surface area (m ² / g) 123 74 38 <1 Inorganic dispersion structure 3D network 2D network Independent particles -

The physical properties of the ion conductors (la) to (4a) impregnated with the aqueous electrolyte solution (1) are shown in Table 2, and the physical properties of the ion conductors (1b) to (4b) impregnated with the organic electrolyte solution (2) are shown in Table 3. .

TABLE 2

Example 1 Example 2 Example 3 Comparative Example 1 Ion Conductor (1a) Ion Conductor (2a) Ion Conductor (3a) Ion Conductor (4a) Contains inorganic ingredients SiO ₂ Al ₂ O ₃ ZrO ₂ - Electrolytic solution impregnation rate (mass%) 810 720 640 250 Ion Conductivity (S / cm) 1.6 × 10 ^-1 1.1 × 10 ^-1 9.8 × 10 ^-2 8.9 x 10 ^-4 Display medium reflectance (%) 96 92 95 79

 TABLE 3

Example 4 Example 5 Example 6 Comparative Example 2 Ion Conductor (1b) Ion Conductor (2b) Ionic Conductor (3b) Ion Conductor (4b) Contains inorganic ingredients SiO ₂ Al ₂ O ₃ ZrO ₂ - Electrolytic solution impregnation rate (mass%) 790 630 610 240 Ion Conductivity (S / cm) 3.0 × ^10-3 2.4 x 10 ^-3 2.2 x 10 ^-3 1.2 × 10 ^-4 Display medium reflectance (%) 95 90 94 73

The ion conductor of the present invention can impregnate a very large amount of electrolyte solution, and the electrolyte solution does not leak from the ion conductor even when pressure is applied. On the other hand, the ion conductors 4a and 4b of Comparative Examples 1 and 2, in which the organic polymer fine particles did not contain ultrafine particles of the inorganic compound, had a low electrolyte impregnation amount and leaked when the pressure was applied.

As shown in Tables 2 and 3, the ion conductors (1a) to (3a) and (lb) to (3b) of the present invention contained 600% by mass or more of the electrolyte solution with respect to the organic polymer fine particles without distinguishing between the aqueous electrolyte solution and the organic electrolyte solution. It could be impregnated without leaking. Moreover, the ion conductivity of all showed the high value of 2x10 <^-3> S / cm or more. On the other hand, in the ion conductors 4a and 4b which do not contain the ultrafine particles of the inorganic compound, the amount of the electrolyte solution to be impregnated was small and the ion conductivity was also low.

In the synthesis of the wet cake 4, the electrolyte solution impregnation amount of the wet cake 4 'produced by mixing 50% by mass of ZnO powder having an average particle diameter of about 2 µm was 230% by mass with respect to the fine particles of the organic polymer. It was almost the same as the wet cake (4) containing no compound. From this, it was found that the inclusion of the inorganic compound particles of the micron order contributes little to the increase in the amount of the electrolyte solution impregnation, and it is important that the organic polymer fine particles contain the ultrafine particles of the inorganic compound of 500 nm or less.

(Manufacture of Electrochemical Display Device and Display Device)

(Example 7)

On both sides of the ion conductor 1a obtained in Example 1, the electrode surface was inward on an ITO electrode (EHC Co., Ltd. product, surface resistance 10Ω / □) having a glass substrate having a thickness of 700 μm. The display element was produced by inserting in 600 micrometer thickness, and sealing the surroundings with an epoxy resin. The display device was produced by connecting the ITO electrode of the said display element to the power supply with a function generator. The various display characteristics described above were evaluated using this display device.

(Example 8)

A display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 2a obtained in Example 2 was used instead of the ion conductor 1a, and various display characteristics were evaluated.

(Example 9)

A display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 3a obtained in Example 3 was used instead of the ion conductor 1a, and various display characteristics were evaluated.

(Example 10)

A display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 1b obtained in Example 4 was used instead of the ion conductor 1a, and various display characteristics were evaluated.

(Example 11)

A display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 2b obtained in Example 5 was used instead of the ion conductor 1a, and various display characteristics were evaluated.

(Example 12)

A display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 3b obtained in Example 6 was used instead of the ion conductor 1a, and various display characteristics were evaluated.

Comparative Example 3 (Aqueous Electrolyte)

A display element and a display device were fabricated in the same manner as in Example 7 except that the ion conductor 4a having no ultrafine particles of the inorganic compound obtained in Comparative Example 1 was used instead of the ion conductor la, and evaluation of various display characteristics was carried out. Carried out.

(Comparative Example 4) (Organic Electrolyte)

In place of the ion conductor 1a, a display element and a display device were fabricated in the same manner as in Example 7, except that the ion conductor 4b having no ultrafine particles of the inorganic compound obtained in Comparative Example 2 was used to evaluate various display characteristics. Carried out.

(Comparative Example 5) (Good quality paper)

As the ion conductor, a display device having the same aqueous electrolyte solution as in Example 7 was fabricated except that the supernatant paper impregnated with the electrolyte solution 1 using water as a solvent was used instead of the organic polymer fine particles so as to have a thickness of 600 µm.

(Comparative Example 6)

The two electrodes are sealed with a resin spacer so that the distance between the two electrodes is 600 μm, leaving two hole portions with an epoxy resin and sealing the surroundings, and after injecting the electrolyte solution 1 into one of the two holes, Example 7 Except having filled the electrolyte solution by sealing a hole with an epoxy resin, and installing the sheet | seat of the wet cake 1 obtained by the synthesis example 1 in the lower side (opposite side of a viewing surface) of the opposing base material 6 in FIG. In the same manner as described above, a display device in which an aqueous electrolyte was encapsulated in a liquid state was manufactured.

(Comparative Example 7)

According to Example 4 of Patent Document 3, by using a mixture of polyvinylidene chloride, LiBF _4, AgClO ₄ as a high molecular solid electrolyte, to prepare an electro deposition type display device.

The following items were evaluated about the electrochemical display element produced by each said Example and the comparative example.

(Measurement and calculation of white reflectance of display element)

Each display element was installed on a standard black plate, and the reflectance (white reflectance) without a voltage was measured by the display device evaluation system DMS-5000 (manufactured by Otronic).

(Observation of the texture)

From the viewpoint of how close the texture of the display portion was to the good quality paper in the state where the white reflectance of each display element was measured, it was visually judged in three steps. A is close to good quality, B is slightly closer to good quality, and C is clearly different from good quality.

(Measurement, calculation of contrast)

An electric field of -1.5 V / mm was continuously applied to each display element for 2 seconds. As a result, the viewing side of the display device changed to black as the metal precipitated. Application of the electric field was stopped in this state, and the reflectance (black reflectance) of the obtained black display was measured and calculated in the same manner as the white reflectance. The obtained black reflectivity and white reflectance were shown by ratio, and this ratio was made into contrast. If the contrast is 10: 1 or more, it can be said that it is sufficient display characteristics. Further, when an electric field of +1.5 V / mm was continuously applied to the black colored display device for 2 seconds, black disappeared in all of Examples 7 to 12 and returned to the initial reflectance state.

(Judgment of electrolyte leakage)

Determination was made in three stages as the electrolyte leakage property from the viewpoint of whether the display element was destroyed and the electrolyte solution leaked out. A will not leak electrolyte, B will leak slightly, C will leak.

Table 4 summarizes the evaluation results of the display characteristics of the obtained display device.

TABLE 4

Ion conductor Reflectance (%) Texture Contrast Electrolyte Leakage Example 7 Ion Conductor (1a) 64 A 12: 1 A Example 8 Ion Conductor (2a) 63 A 11: 1 A Example 9 Ion Conductor (3a) 63 A 12: 1 A Example 10 Ion Conductor (1b) 62 A 12: 1 A Example 11 Ion Conductor (2b) 62 A 11: 1 A Example 12 Ion Conductor (3b) 61 A 12: 1 A Comparative Example 3 Ion Conductor (4a) 38 B 3: 1 B Comparative Example 4 Ion Conductor (4b) 36 B 3: 1 B Comparative Example 5 Electrolyte Impregnated Paper 38 B 2: 1 C Comparative Example 6 Electrolyte 31 C 3: 1 C Comparative Example 7 Polyelectrolyte 67 C 5: 1 A

In addition, as shown in Table 4, the display device fabricated using the ion conductor according to the present invention has a high contrast of 60% or more, close to the texture of paper, and high contrast because the ion conductor has high ion conductivity. It turned out to be. Compared with the comparative example 7 which uses the polymer solid electrolyte as a medium for display elements, the small-coloration speed (responsiveness) and the blackness at the time of coloring were also excellent. In Comparative Example 7, the reflectance was relatively high, but the texture was significantly different from that of paper. On the other hand, in Comparative Example 5, since the member inside the element does not have sufficient electrolyte impregnation force, since uniform ion migration in the electrolyte does not occur sufficiently, uniform uneven coloration does not occur smoothly over the entire surface of the device display surface. The contrast ratio was very low. In Comparative Example 6, the high reflectance of the wet cake on the back side was largely attenuated by the incident light passing through the two glass substrates, the two-layer ITO electrode, and the electrolyte solution on the front side in a reciprocating manner.

As mentioned above, it turned out that the ion conductor of this invention has the outstanding characteristic also as an ion conductor and the medium for electrochemical display elements by the result of Tables 1-4.

The ion conductor of the present invention has a very high ion conductivity and can be used as a member of an electrochemical device such as a secondary battery, an electric double layer capacitor, or a solar cell.

In addition, since visibility and texture are very close to paper, it can be suitably used as an ion conductor for a reflective electrochemical display element.

Claims (10)

It consists of the microparticles of the organic polymer containing the ultrafine particle of 20-80 mass% of inorganic compounds, and the electrolyte solution impregnated in the microparticles of the said organic polymer, The ultrafine particle of the said inorganic compound has an average particle diameter of 500 nm or less, The fine particle of an organic polymer has a specific surface area by BET method of 30 m <^2> / g or more, The ion conductor characterized by the above-mentioned. The method of claim 1, The ion conductor whose impregnation rate of the said electrolyte solution with respect to the microparticles | fine-particles of the said organic polymer is 500-2000 mass%. The method of claim 1, The ion conductor in which the microparticles | fine-particles of the said organic polymer have an average particle diameter of 1-1000 micrometers. The method of claim 1, An ion conductor having fine particles of the organic polymer having an average short diameter of 20 μm or less and an average aspect ratio of 5-20. The method of claim 1, An ion conductor, wherein the inorganic compound is at least one inorganic compound selected from the group consisting of metal oxides, metal hydroxides and metal carbonates. The method of claim 1, An ion conductor, wherein the organic polymer is at least one organic polymer selected from the group consisting of polyamide, polyurethane, and polyurea. The method of claim 5, The organic solution (A) in which the fine particles of the organic polymer contain at least one compound selected from the group consisting of dicarboxylic acid dihalide, dihaloformate and phosgene and an organic solvent, Aqueous solution containing metal compound, diamine, and water of at least one alkali metal element and other metal elements (B) Ion conductor obtained by interfacial polycondensation caused by contact with Electrochemistry consisting of two electrode plates, the ion conductor of claim 1 held between the two electrode plates, and a material reversibly discolored by an electrochemical redox reaction caused by ion conduction in the ion conductor. Type display element. The method of claim 8, An electrochemical display device, wherein the material reversibly discolored by the electrochemical redox reaction is a colorant contained in the ion conductor. The method of claim 8, An electrochemical display device, wherein a material reversibly discolored by the electrochemical redox reaction constitutes a chromophore layer provided on the electrode plate.

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