WO2003046653A1

WO2003046653A1 - Electrolyte and electrochromic device

Info

Publication number: WO2003046653A1
Application number: PCT/JP2002/012444
Authority: WO
Inventors: Shinji Ohshima; Masaki Minami; Junichiro Tanimoto; Takaya Kubo; Yoshinori Nishikitani
Original assignee: Nippon Oil Corporation
Priority date: 2001-11-29
Filing date: 2002-11-28
Publication date: 2003-06-05

Abstract

An electrolyte enabling manufacture of an electrochemical device by a simple method, exhibiting a high ion conductivity, free from troubles such as liquid leakage, excellent in fire retardance, transparency, and applicable to various uses, and containing a support electrolyte, an organic solvent, and a basic amine compound. Further there is provided an electrochromic device having two transparent conductive substrates between which an electrolyte layer is interposed, wherein an electrochromic layer is provided to at least one of two transparent conductive substrates, and the electrolyte layer contains a basic amine compound. Therefore, the device performances such as the coloring/discoloring response and durability are improved irrespective of the physical properties of the electrochromic layer.

Description

Description Electrolyte and electrochromic element

[Technical field]

The present invention relates to an electrolyte applicable to various electrochemical devices such as all-solid-state secondary batteries, wet-type solar cells, electric double-layer capacitors, electrolytic capacitors, and electrochromic devices at the electoral port.

In addition, the present invention relates to an electric-port chromic element useful for various uses such as a display element and light control glass.

[Background technology]

Conventionally, when manufacturing various types of electrochemical devices such as primary batteries and secondary batteries, a so-called electrolyte containing an organic solvent such as propylene carbonate as the main component is used to form a solid electrolyte between two electrodes. However, there is a problem that the liquid may be scattered due to damage of the element during use, or the liquid may leak during use.

Solid electrolytes such as a solid polymer electrolyte have been proposed as means for improving these disadvantages. In recent years, a solid polymer electrolyte using polyvinylidene fluoride has been proposed. For example, Japanese Unexamined Patent Publication (Kokai) No. Hei 8-5507407 discloses a lithium salt solution comprising a polyvinylidene fluoride-hexafluoropropylene copolymer and comprising a medium boiling point solvent in the film. There has been proposed a solid electrolyte for a lithium-ion battery containing the same uniformly. However, the polyvinylidene fluoride-hexafluoropropylene copolymer may contain a small amount of hydrogen fluoride depending on the production conditions, and this may cause a problem in the durability of the electrochemical element. Sometimes occurred. As a method for removing hydrogen fluoride contained in the copolymer, polyvinylidene fluoride-hexafluoropropylene copolymer is dissolved in a good solvent such as DMF or acetone, and reprecipitated in a solvent such as water or alcohol. Although there is a method, it requires extremely complicated operations, and this leads to an increase in cost for industrial implementation. When applied to devices without removing a trace amount of hydrogen fluoride contained in the copolymer, the durability of various secondary batteries, wet solar cells, electric double-layer capacitors, electrolytic capacitors, electrochromic devices, etc. In an electrochemical device that requires, the solvent may be hydrolyzed, and it may be difficult to maintain the initial performance.

The present invention has been made in view of such circumstances, and has as its object to manufacture an electrochemical element by a simple method, to have high ionic conductivity, and to improve the durability of the element. To provide electrolytes that can be deployed in many applications.

In addition, there are various types of electrochromic devices applied to various dimming devices and display devices. For example, a transparent conductive substrate, an electoric chromic layer, an electrolyte, and a transparent conductive substrate (counter electrode) are sequentially arranged. The configuration provided is a typical one.

In such an electrochromic device, the basic device performance is largely affected by the film physical properties of the electrochromic layer. For example, the elect port chromic layer, the reduction coloring type elect port chromic case substances are used, oxidation evening tungsten (wo ₃₎ The film is typically deposited decoloring response of the elements, photochromic click properties , affected by the W 0 ₃ of film properties for performance such as durability.

W_〇 ₃ film, a problem usually, a sputtering method, that can be produced by a vacuum deposition method such as electron beam vacuum deposition number, changes in membrane material properties by differences in environment and conditions at the time of vacuum deposition occurs There was a point.

Further, it is known that the wo ₃ film has a solid acid catalyzing ability. Therefore, there is a disadvantage that the constituent members of the electrolyte layer are deteriorated depending on the use conditions and the type of the electrolyte layer.

Therefore, from an industrial point of view, it is not affected by the film physical properties of the electoric chromic layer, it can suppress the device deterioration due to the solid acid catalysis of the electrochromic film, and it has excellent response to coloration and decoloration. There has been a demand for the development of an electronic aperture chromic element with improved durability.

The present invention does not depend on the film physical properties of an electrochromic film by adding a specific basic substance to an electrolyte in an electrochromic element having an opening. Ku, thereby improving the device performance such as Chakushoiro response and durability can be suppressed element degradation by solid acid catalyzed even when using the W 0 ₃ layer as elect port electrochromic layer Elec Torokuromikku An element is provided. [Disclosure of the Invention]

The present inventors have made intensive studies to solve the conventional problems as described above, and as a result, have completed the present invention.

That is, the present invention relates to an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound.

Further, the present invention relates to an electrolyte comprising a supporting electrolyte, an organic solvent and a basic amine compound in a polymer matrix.

In the electrolyte of the present invention, the polymer matrix is preferably a polyvinylidene fluoride-based polymer compound.

In the electrolyte of the present invention, it is preferable that the basic amine compound is a tertiary amine.

In the electrolyte of the present invention, the content of the basic amine compound is preferably 1 mass ppm to 1000 mass ppm with respect to the mass of the electrolyte.

In the electrolyte of the present invention, it is preferable that the organic solvent is a solvent containing a phosphate compound or a phosphate compound.

Further, the present invention is an electoric chromic element in which an electrolyte layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer. Further, the present invention relates to an electrochromic device, wherein the electrolyte contains a basic amine compound. In the electrochromic device of the present invention, the basic amine compound is preferably a tertiary amine.

In the electoral chromic device of the present invention, the electrolyte is preferably an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound. In the electoric chromic device of the present invention, the electrolyte may be a polymer matrix containing a supporting electrolyte, an organic solvent, and a basic amine compound. Preferably, it is quality.

In the electrochromic device of the present invention, the polymer matrix is preferably a polyvinylidene fluoride-based polymer compound.

In the electrochromic device of the present invention, the content of the basic amine compound is 1 mass ρρπ! Preferably it is ~ 10000 mass ppm.

In the electrochromic device of the present invention, it is preferable that the organic solvent is a phosphate ester-based compound or a solvent containing a phosphate ester-based compound. In the electrochromic device of the present invention, the electrochromic layer is made of tungsten oxide. Is preferred. Hereinafter, the present invention will be described in detail.

The present invention relates to an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound.

Further, the present invention relates to an electrolyte comprising a supporting electrolyte, an organic solvent, and a basic amine compound in a polymer matrix. As the polymer matrix, a vinylidene fluoride polymer compound is preferably used.

As the supporting electrolyte used in the present invention, salts, acids and alkalis usually used in the field of electrochemistry or batteries can be used.

The salt is not particularly limited, and examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, and quaternary phosphonium salts. Salts are preferred.

Specific examples of the salts include halogen ions, S CN @ -, C 10 ₄ one, BF ₄ _{_{one, CF 3 S0 3 \ (CF}} 3 S0 2) 2 N-ヽ_{_{_{(C 2 F 5 S0 2)}}} 2 N -, PF ₆ -, AsF ₆ -ヽ_{_{CH 3 COO-, CH 3 (C}} fj H 4) S0 3 -, and _{_{_{(C 2 F 5 S0 2)}}} L i salts with selection Bareru pair Anion from ₃ C, Na salt, Alternatively, a K salt may be mentioned, and a Li salt is particularly preferred. For _{example, L i C10 4, L i} S CN, L iBF 4, L i As F ri L i CF 3 S0 3, L iPF ( have L il, Na l, NaSCN, NaC 10 4, N aBF ₄ , NaAs F ₆ , KS CN, KC 1 and the like can be exemplified.

The halogen ions, SCN-, C 10 ₄ _{_{one, BF 4 -, CF 3 S0}} 3 -, (CF 3 S0 2) 2 N-, (C 2 F 5 S0 2) 2 N-, PF 6 -, As F _{_{6 -, CH 3 COO_, CH}} 3 (C 6 H 4) S0 3 -, and _{_{_{(C 2 F 5 S0 2)}}} 4 grade Anmoniumu salt having a pair Anion selected from ₃ C-, specifically, (CH ₃ ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBF ₄ , (n-C ₄ H _g ) ₄ NBF ₄ , (C ₂ H ₅ ) ₄ NBr, (CH ₃ ) ₄ NS0 ₃ CF ₃ s (C ₂ H ₅ ) ₄ NS0 ₃ CF ₃ , (n— C ₄ H ₉ ) ₄ NS0 ₃ CF ₃ , (C ₂ H ₅ ) ₄ NC 10 ₄ , (nC ₄ H ₉ ) ₄ NC.10 ₄ , CH ₃ ( C ₂ H ₅ ) ₃ NB F ₄ , (CH ₃ ) ₂ (C ₂ H ₅ ) ₂ NBF ₄ , and even

And the like.

The halogen _{ions, SCN-, C 10 4 -,} BF 4 -, CF 3 S0 3 -ヽ_{_{_{(CF 3 S0 2) 2 N}}} -, (C 2 F 5 S0 2) 2 N-ヽPF _6, A s F _fi- , CH ₃ C 00-, C

Anion selected from H ₃ (C _fi H,) S0 ₃ and (C ₂ F ₅ S0 ₂ ) ₃ C— Phosphonium salts having, specifically, (CH ₃ ) ₄ PBF ₄ , (C ₂ H ₅ ) ₄ PBF ₄ , (C ₃ H ₇ ) ₄ PBF ₄ , (C ₄ H ₉ ) ₄ PBF _{4 and the} like. Can be

Further, these mixtures can also be suitably used. The acids are not particularly limited, and various inorganic and organic acids such as sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids can be used.

The alkalis are not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used. The amount of the supporting electrolyte used is arbitrary, but usually, it is preferably 0.01 M or more, preferably 0.05 M or more, more preferably 0.1 M or more in the organic solvent. On the other hand, it is usually 20 M or less, preferably 10 M or less, and more preferably 5 M or less.

The electrolyte generally contains 0.01% by mass or more, preferably 0.1% by mass or more, and usually 20% by mass or less, and preferably 10% by mass or less. Next, the organic solvent will be described.

As the organic solvent, any of the solvents generally used for electrochemical cells and batteries can be used. Specifically, phosphoric ester compounds, acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphonamide, ethylene carbonate, dimethoxane, and acetonitrile Butyrolactone, avalerolactone, sulfolane, dimethyloxetane, propionitrile, glulononitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulpholane, polyethylene Glycols and the like can be used. Particularly, phosphate ester compounds, propylene carbonate, ethylene carbonate, Dimethylsulfoxide, dimethoxene, acetonitrile, abutyrolactone, Sulfolane, dioxolan, dimethylformamide, dimethoxetane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolan, sulfolane, trimethylphosphate, polyethylene glycol and the like are preferred. As the solvent, one kind may be used alone, or two or more kinds may be used in combination. Further, a phosphoric ester compound or a solvent containing the phosphoric ester compound can also be used as a suitable compound. Specific examples of the phosphate compound include trimethyl phosphate triethyl phosphate, tripropyl phosphate, ethyl dimethyl phosphate, triptyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, and phosphorus Examples thereof include trioctyl acid, trinonyl phosphate, tridecyl phosphate, tris (trifluoromethyl) phosphate, tris (pentafluoroethyl) phosphate, and triphenyl phosphate. Preferably, triethyl ester and trimethyl phosphate are preferable. preferable. Also, two or more of these can be used. The amount of the solvent used is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more in the electrolyte, and the upper limit is usually 98% by mass, preferably 95% by mass. %, More preferably 90% by mass or less. Next, the basic amine compound will be described.

The basic amine compound used in the present invention functions as a proton acceptor in the electrolyte, and usually has a pKa of the conjugate acid in an aqueous solution at 25 ° C and an aqueous solution of 4 to 12, preferably 5 to 11. Those in the range can be mentioned. Examples of such basic amine compounds include primary amines (RNH ₂ ), secondary amines (: R ₂ NH), tertiary amines (R ₃ N) and derivatives thereof. it can. In addition to these monoamines, polyamines such as diamine, triamine, and tetraamine can also be used. R represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and may be the same or different. Such a hydrocarbon group may be linear, branched, cyclic, saturated, or unsaturated, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and an alkylaryl group. , Specifically, methyl, ethyl, propyl, butyl Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, penzyl group, naphthyl group, etc. . Specific compounds include, for example, triethylamine, trimethylamine, tripropylamine, triptylamine, trihexylamine, triphenylamine, getylamine, dimethylamine, dipropylamine, dibutylamine, dihexylamine, tetramethylethylenediamine, tetramethylbenzidine. , N: N 'over diphenyl benzidine, Kishiruamin Jechiruamin, Jifue two Ruamin, Mechiruami down, Puropiruamin, butylamine, to di, Fueniruamin, 2 Nafuchiruamin, pyridine, 4, 4 ⁵ - Bibirijiru, 2, 2, one Bibirijiru, 2 : 6-Lutidine, 3,4-lutidine, 4-dimethylaminopyridine, quinoline, 2-methylquinoline, isoquinoline, quinazoline, 1,3,5-triazine, 1,2,4-triazolate , Imidazole, aniline, N-methylaniline, N, N-dimethylaniline, 2,3-dimethylaniline, 2,6-dimethylaniline, pyrrole, carbazole, N-methylcarbazole, piperidine, 1-methylbiperidine , Piperazine, 1-methylbiperazine, 1,4-dimethylbiperazine and the like. Particularly preferred are tertiary amines such as triethylamine, triphenylamine, pyridine, 4,4-bipyridyl, 2,6-lutidine and isoquinoline. The amount of the basic amine compound is not particularly limited and may be appropriately selected, but is usually preferably 1 ppm by mass or more, more preferably 10 mass ppm or more, and particularly preferably, based on the total mass of the electrolyte. Is 50 mass ppm. On the other hand, it is preferably at most 10,000 mass ppm, more preferably at most 5,000 mass ppm, particularly preferably at most 1,000 mass ppm. When the amount of the basic amine compound is less than 1 mass ppm, the effect of suppressing the hydrolysis of the solvent may be poor. May occur. The electrolyte of the present invention, ion conductivity, usually at room temperature 1 X 1 0- ⁷ S / cm or more, preferably 1 X 1 0 - 6 S / cm or more, more preferably ^{1 X 1 0 - 5 S /} cm The following is shown. Ionic conductivity can be determined by a general method such as the complex impedance method. Next, the polyvinylidene fluoride polymer compound preferably used as the polymer matrix in the present invention will be described.

Examples of the polyvinylidene fluoride-based high molecular compound used as the polymer matrix in the present invention include a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride with another polymerizable monomer, preferably a radical polymerizable monomer. Copolymers are exemplified. Examples of other polymerizable monomers to be copolymerized with vinylidene fluoride (hereinafter, referred to as copolymerizable monomers) include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile. , Vinylidene chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene and the like.

These copolymerizable monomers can be used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of vinylidene fluoride. Also, two or more of these copolymerizable monomers can be added. For example, copolymerization may be carried out using a combination of vinylidene fluoride + hexafluoropropylene + tetrafluoroethylene, vinylidene fluoride + tetrafluoroethylene + ethylene, vinylidene fluoride + tetrafluoroethylene + propylene, and the like.

Hexafluoropropylene is preferably used as the copolymerizable monomer. In the present invention, in particular, a vinylidene fluoride-hexafluoropropylene copolymer obtained by copolymerizing 1 to 25% by mass of hexafluoropropylene with vinylidene fluoride is preferably used as a solid electrolyte having a high molecular matrix. Can be. Further, two or more kinds of vinylidene fluoride-hexafluoropropylene copolymers having different copolymerization ratios may be mixed and used.

Usually, these vinylidene fluoride-hexafluoropropylene copolymers are used during polymerization. Contains hydrogen fluoride due to decomposition of the monomer. Most of the hydrogen fluoride is removed by water washing, but remains in a trace amount, and is usually contained in an amount of about 10 to 100 ppm by mass, more typically on the order of tens of ppm.

Further, in the present invention, one kind of a polymer compound selected from a polyacrylate-based polymer compound, a polyacrylonitrile-based polymer compound and a polyether-based polymer compound is used as the polymer matrix in the polyvinylidene fluoride-based polymer compound. It is also possible to use a mixture of two or more kinds. The other polymer compound mixed with the polyvinylidene fluoride polymer compound is preferably 50% by mass or less.

The number average molecular weight of the polyvinylidene fluoride-based polymer compound used in the present invention is usually 10, 00 0 to 2, 0 0 0, 0 0 0, preferably 10 0, 0 0 0 Those having a range of 11, 0000, 0000 can be suitably used.

When a polyvinylidene fluoride polymer compound is used as the polymer matrix, the above-mentioned various organic solvents can be combined as the organic solvent. Among them, particularly, the phosphate ester compound or the phosphate ester compound A solvent containing is preferred. In this case, the amount of the solvent used is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, and 80% by mass or less, preferably 70% by mass in the electrolyte. It is desirable to include the following amount. Next, a method for producing a solid electrolyte using a polyvinylidene fluoride polymer compound as a polymer matrix will be described.

Such a solid electrolyte can be easily obtained by forming a polyvinylidene fluoride polymer compound, a supporting electrolyte, an organic solvent, and a basic amine compound into a desired shape, for example, a sheet-to-film shape by a known method. I can do it. The method in this case is not particularly limited, but a method obtained in a film state by a casting method can be preferably mentioned.

For the casting method, a polymer matrix and an electrolyte solution are mixed, the viscosity is adjusted with an appropriate diluent, and the film is formed by coating and drying with the usual coating method used for the casting method. Can be. As for the night, the nights are: Doctor Ko, Brako, Koko, Koto, Knife, Yu, River Throrko, Gravure Evening, Sprayco and Curtainco can be used, and can be used depending on viscosity and film thickness. The film thickness can be adjusted by a coating apparatus, and it is usually preferable that the film thickness be 25 / m or more. The upper limit of the film thickness is not particularly limited and may be arbitrarily selected. For example, when the film is manufactured by a casting method, the upper limit is usually about 500 m. The amount of the solvent in the solid electrolyte can be appropriately adjusted by selecting the drying conditions.

When a solid electrolyte is applied to various types of electrochemical devices, the shape and thickness of the solid electrolyte layer are appropriately selected depending on the application depending on the type of the device and are not particularly limited, but the thickness is usually lm or more. Preferably, it is particularly preferably at least 10 μm. On the other hand, it is preferably at most 3 mm, particularly preferably at most 1 mm.

In addition, the solid electrolyte of the present invention can be a stiff film, in which case its tensile modulus at 25 ° C. is preferably 5 × 10 ⁴ N / m ² or more. the ^{1 X 1 0 5 N / m} 2 or more, and most preferably it is desirable to have a characteristic is ^{5 X 1 0 5 N / m} 2 or more. Incidentally, the tensile modulus, tensile test machine generally used, 2 cm X 5 by strip-shaped sample of cm is the value of the case having conducted the measurement _c Also, the present invention is, two transparent conductive substrates An electrochromic element in which an electrolyte layer is sandwiched, wherein at least one of the conductive substrates has an electrochromic layer, and the electrolyte contains a basic amine compound. The present invention relates to an electrochromic element.

Two transparent conductive substrates are used in the electorifice chromic device of the present invention. Here, the transparent conductive substrate means a transparent substrate that functions as an electrode. The conductive substrate according to the present invention includes a substrate in which the substrate itself is made of a conductive material, and a laminate in which an electrode layer is laminated on one or both sides of a substrate having no conductivity. Regardless of whether or not it has conductivity, the substrate itself preferably has a smooth surface at room temperature, but that surface may be flat or curved, It may be deformed.

In general, an electrochromic element in which both conductive substrates are transparent is suitable for a display element or light control glass. The transparent conductive substrate is usually manufactured by laminating a transparent electrode layer on a transparent substrate. Here, “transparent” means having a light transmittance of 10 to 100% in the visible light region, and there may be a partially opaque portion.

The material of the transparent substrate is not particularly limited, and may be, for example, colorless or colored glass, reinforced glass, or the like, and may be colorless or colored transparent resin. Specific examples of the transparent resin referred to here include polyethylene terephthalate, polyethylene naphtholate, polyamide, polysulfone, polyethersulfone, polyether-teretone, ketone, bolifenylene sulfide, polycarbonate, polyimide, Polymethyl methacrylate, polystyrene and the like.

The transparent electrode layer is not particularly limited as long as the object of the present invention is achieved, and examples thereof include a metal thin film such as gold, silver, chromium, copper, and tungsten, and a conductive film made of a metal oxide. As the metal oxide, such as tin oxide, zinc oxide, and vanadium oxide, Indium Tin Oxide (IT 0 ( I n 2 0 3: S n)) doped with minor components thereto, Fluorine doped Tin Oxide (FTO ( _{Sn0 2: F)), Aluminum} doped Zinc Oxide (AZ 0 (ZnO: a 1)) or the like is used as a preferable example. The thickness of the electrode layer is usually 100 to 5000 μm, preferably 500 to 3000 μm. The surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention, but is usually 0.5 to 500 Ω / sq, preferably 2 to 5 Ω / sq.

The method for forming the transparent electrode layer is not particularly limited, and a known method is appropriately selected and used depending on the type of the above-described metal or metal oxide used as the conductive layer. Usually, a vacuum evaporation method, an ion plating method, or the like is used. Method, CVD or sputter ring method, sol-gel method, etc. are used. In either case, it is desirable to form the substrate at a substrate temperature of 20 to 700 ° C.

The present invention is characterized in that at least one of the conductive substrates has an electrochromic layer. The electrochromic layer is formed on a conductive substrate on a conductive substrate.

The material forming the electoric chromic layer may be any of an oxidative coloring type electrochromic compound and a reducing coloring type electrochromic compound. Examples thereof include an inorganic compound of a metal oxide and various organic electrochromic compounds, and are not particularly limited. In particular, an inorganic electochromic compound is preferable. In concrete terms, tungsten oxide (wo _3), vanadium oxide, molybdenum oxide, acid iridium, nickel oxide, titanium oxide, chromium oxide, manganese oxide, transition metal oxides and the ratio thereof of any such oxide cobalt The oxide film included in the above. As a film forming method, a wet method such as a sol-gel method or an electrochemical method, or a vacuum film forming method such as an evaporation method, a sputtering method, an ion plating method, or a pulse laser deposition method can be used.

The thickness of the chromic layer at the opening is not particularly limited, but is usually about 0.1 to 2 / m, preferably about 0.4 to 0.8 zm.

The electrochromic device of the present invention has an electrochromic layer on at least one side of the conductive substrate. The transparent conductive substrate facing the conductive substrate having the electrochromic layer includes (a) In addition to the configuration using a conductive substrate, (b) a configuration using a conductive substrate having another electrification port chromic layer, and (c) a member in which conductive fine particles are bound on a conductive surface of the conductive substrate with a binder. May be arranged so that the light transmittance (or light reflectivity) required for the entire counter electrode is not impaired.

The form (c) is specifically described in, for example, Japanese Patent Application Laid-Open Nos. Hei 6-28190 and Hei 10-239719.

In the case where the electrochromic layer is disposed on both the conductive substrates, if one of the electrochromic layers is an oxidizing electrochromic layer, the other is a reducing electrochromic layer, and the other is an electrochromic layer. When is a reducing electrochromic layer at the opening, it is preferable to use an oxidizing electrochromic layer at the other side. For example, in the case where one of the electoric chromic layers is a tungsten oxide layer, the electoric chromic layer of the other (counter electrode side conductive substrate) is not particularly limited, but may be nickel oxide, chromium oxide, or the like. Preferred examples of the electrochromic device of the present invention include manganese oxide, cobalt oxide, iridium oxide, and Prussian blue. On the conductive surface of the conductive substrate facing the conductive substrate having the electrochromic layer, Conductive fine particles with a binder It is preferable that a bound member is arranged.

Such conductive fine particles, usually 10- ⁸ S · cm one ¹ or more, preferably 10- ⁵ S - cm- ¹ or more, more preferably Ru substance der showing a 10- ² S · cm- ¹ or more conductive It is desirable.

These conductive fine particles usually have an electric capacity of 1 farad / g or more, preferably 5 farads / g or more, more preferably 10 farads / g or more, or 1 clone / g or more. Preferably, it can store a charge amount of preferably 5 coulombs / g or more, more preferably 10 clones / g or more.c As a material constituting such fine particles, for example, porous carbon, the fin evening one Kareshon material, conductive fine particles having a 1 Fara' de / g or more electric capacity of the present invention that the conductive polymer compound, or mixtures thereof, if example embodiment, the surface area is typically, 10 m ² / g or more, preferably 50 to 500 Om ² / g, particularly preferably 300 to 4000 m ² / g. Limit Those are in is not the name. Such activated carbon can be obtained, for example, by a method of carbonization activation of palm, petroleum pitch, phenolic resin, rayon fiber, polyacrylonitrile fiber, and the like.

Examples of the conductive fine particles capable of storing an electric charge of 1 clone / g or more according to the present invention include an in-situ radiation material, a conductive polymer compound, and the like. Materials that can be stored are preferred.

As the fin evening Ichiriki Reshiyon material, disulfides such as a known _{_{T i S 2, Mo S 2}} ; C o 0 2, N i 0 dioxide such as _{_{_{2; W 18 0 49, W}}} 20 O 58 And the like.

On the other hand, examples of the conductive polymer compound include a conductive polymer compound containing polyalinine, polythiophene, polypropylene, polyphenylenevinylene, polyacene, or the like as a main component and obtained by doping or the like.

The particle size of the fine particles is not particularly limited as long as the object of the present invention is not impaired, but is usually 500 m to 0.1 m, preferably 200 m to 0.3 m, and more preferably 50 m. An average particle size of Ml in the range of m to 0.5 m is preferred. Next, an electrolyte layer (hereinafter, also referred to as an ion conductive layer) will be described.

In general, the electrolyte layer in the electorifice chromic element has an ion conductivity of 1 × 10 ¹⁷ S / cm or more at room temperature, and plays a role of coloring, decoloring, and discoloring the electoral chromic layer. Such an electrolyte layer can be formed using any of a liquid ion-conductive substance, a gelled liquid ion-conductive substance, and a solid ion-conductive substance. In particular, a solid ion-conductive substance is used. It is desirable.

Liquid ion conductive material

The liquid ionic conductive substance is prepared by dissolving a supporting electrolyte such as salts, acids and alkalis in a solvent.

As the solvent, any of the solvents generally used in electrochemical cells and batteries can be used, and specific examples include the organic solvents described above. The use amount of the solvent is not particularly limited, but usually, the solvent accounts for at least 20% by mass, preferably at least 50% by mass, more preferably at least 70% by mass of the ion-conductive layer. 9 8 wt%, preferably from 9 to 5% by weight, still as preferably _c supporting electrolyte is 9 0 wt% or less, wherein the salts in the field of the field or the battery electrochemical Ru is typically used, acids, alkalis Can be used.

The supporting electrolyte may or may not be used, and when used, the amount of use is arbitrary. In general, the supporting electrolyte is usually 20 M or less in the ion conductive layer, preferably. Is preferably at most 10 M, more preferably at most 5 M, at least 0.1 M, preferably at least 0.05 M, even more preferably at least 0.1 M.

Gelled liquid ion conductive material

The gelled liquid-based ion-conductive substance means a substance obtained by thickening or gelling the above-mentioned liquid-based ion-conductive substance. This substance is obtained by adding a polymer or a gelling agent to the liquid-based ion-conductive substance. Is prepared.

The polymer used for this is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, Polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, nafion and the like can be used.

The gelling agent is also not particularly limited, and oxyethylene methacrylate, oxyshethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used. Solid ion conductive material

A solid ion-conductive substance refers to a substance that is solid at room temperature and has ion conductivity, including polyethylene oxide, a polymer of oxyethylene (meth) acrylate, naphion, polystyrene sulfonic acid, and polystyrene. ether poly Ma one, full Uz Motokei polymers such Porifudzu fluoride polymer, Li ₃ n, n a one ^ one _{_{A1 2 0 3, S n (}} HP 0 4) the use of ₂ · H ₂ 〇 like Can be. In addition, a supporting electrolyte is dispersed in a polymer obtained by polymerizing an oxyalkylene methacrylate compound, an oxyalkylene acrylate 1, or a urea acrylate compound. as a first example of _c the solid polymer electrolyte molecular solid electrolyte can be used, the precursor © Les evening Nakurireto represented by the following general formula (1), the organic solvent, and a composition containing the supporting electrolyte And a solid polymer electrolyte obtained by solidifying this precursor.

In the general formula (1), R ¹ and R ² are the same or different groups and represent a group selected from the following general formulas (2) to (4). R ³ and R ⁴ are the same or different groups, and represent a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms. Y is a polyether unit (_◦—), a polyester unit (one C00—), polycarbonate Unit (-OCOO-) or a mixture of two or more of these units. M represents an integer in the range of 1 to 100, preferably 1 to 50, and more preferably 1 to 20.

In the general formulas (2) to (4), R ^{5 to} R ⁷ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁸ represents a divalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. ¹⁹ represents a trivalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms. R ^1. Represents a tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms.

Examples of the divalent hydrocarbon residue represented by R ³ and R ⁴ in the general formula (1) include a linear divalent hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.

The molecular weight of the urethane acrylate represented by the general formula (1) is not particularly limited, but is preferably 2,500 to 30,000, more preferably 3,000 to 20,000.

The amount of the organic solvent to be added is usually 100 to 1200 parts by mass, preferably 200 to 900 parts by mass, based on 100 parts by mass of the urethane acrylate. If the added amount of the organic solvent is too small, the ionic conductivity is not sufficient, and if the added amount of the organic solvent is too large, the mechanical strength may be reduced.

The supporting electrolyte is appropriately selected depending on the use, etc. The purpose of the solid polymer electrolyte of the present invention, as long as they do not impair the object of the present invention, but are not limited to, those exemplified above ¹ can be mentioned as preferred . The amount of addition is 0.1 to organic solvent. It is 30% by mass, preferably 1 to 20% by mass.

Further, other components can be added as needed, as long as the object of the present invention is not impaired. Such optional components include, for example, a crosslinking agent, a polymerization initiator (light or heat), an ultraviolet absorber, and the like.

As a second example of the polymer solid electrolyte, a composition comprising a monofunctional acryloyl-modified polyalkylene oxide represented by the following general formula (5), a polyfunctional acryloyl-modified polyalkylene oxide, the organic solvent, and the supporting electrolyte And a solid polymer electrolyte obtained by solidifying the precursor.

R ¹¹ _R 12 _R 13

I I I

CH = C— CO- CHCHO- R 14 (5)

ll

O

—In the general formula (5), I ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be the same or different, and R ¹¹ is a hydrogen atom, a methyl group; R ¹² is a hydrogen atom, a methyl group, R ¹³ is a hydrogen atom, a methyl group, and R ¹⁴ is a hydrogen atom, a methyl group, or an ethyl group.

In the general formula (5), n represents an integer of 1 or more, preferably 1 to 100, more preferably 2 to 50, and further preferably 2 to 30.

When n is 2 or more, the oxyalkylene units may have different so-called copolymerized oxyalkylene units.

Preferable examples of the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention include a compound represented by the general formula (6), a so-called bifunctional acryloyl-modified polyalkylene oxide, and a compound represented by the general formula (7). And the so-called polyfunctional acryloyl-modified polyalkylene oxide having three or more functional groups.

CH ₂ (6)

²⁰²¹

CHCHO- L (7)

In the general formula (6), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 or more. In the general formula (7), R ^ig , R ² ° and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, q represents an integer of 1 or more, and r represents 2 to Is an integer of 4, and L represents an r-valent linking group. The linking group L is usually a divalent, trivalent or tetravalent hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms.

Of course, a bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (6) and a trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (7) may be used in combination. When the compound represented by the general formula (6) and the compound represented by the general formula (7) are used in combination, the mass ratio is usually 0.1 to 99.9-99.9 / 0.1, preferably 1/1. A range of 99 to 99/1, more preferably 20/80 to 80/20 is desirable. The mass ratio of the compound represented by the general formula (5) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / ◦.001 to; L / l, preferably 1 / 0.05 to 1 /. It is in the range of 0.5. The compounding ratio of the organic solvent is usually in the range of 50 to 800% by mass, preferably 100 to 500% by mass with respect to the total mass of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide. Is desirable.

The compounding ratio of the supporting electrolyte is usually 1 to 30% by mass, preferably 3 to 20% by mass based on the total mass of the compound represented by the general formula (5), the polyfunctional acryloyl-modified polyalkylene oxide and the organic solvent. % Range.

Further, other components can be added as needed, as long as the object of the present invention is not impaired. Examples of such optional components include, but are not particularly limited to, a photopolymerization initiator for photopolymerization, a thermal polymerization initiator for thermal polymerization, and an ultraviolet absorber. The amount of the polymerization initiator to be used is usually 0.005 to 0.005 mass of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide. It is in the range of 5% by weight, preferably 0.01 to 3% by weight. As a third example of the polymer solid electrolyte, a composition containing the organic solvent and the supporting electrolyte in a polymer matrix composed of a polyvinylidene fluoride-based polymer compound is used as a precursor. And the solid polymer electrolyte obtained by solidifying the polymer. In the present invention, the thickness of the ion conductive layer is not particularly limited, but is usually 20 / π!範囲 1 mm, preferably in the range of 50-500 μm. The present invention is characterized in that the ion conductive layer contains a basic amine compound. As the basic amine compound, the above-described basic amine compounds can be used.

The amount of the basic amine compound is 1 mass ρ ρ π! 1100000 mass ppm. It is preferably from 10 to 500 mass ppm, particularly preferably from 50 to: L000 mass ppm.

When the content of the basic Amin compound is less than 1 ppm by weight, the addition effect is not sufficient, and if the content of the basic Amin compound is more than 1 0 0 0 0 ppm by weight, W 0 ₃ film It is not preferable because phenomena such as elution may occur, which may have an adverse effect.

By blending a basic amine compound in the ion conductive layer, excellent effects such as a significant improvement in the durability of the electoric chromic element can be achieved without being affected by the film physical properties of the electoric chromic layer. It can be expressed, but this is presumed to have the effect of suppressing the hydrolysis reaction of the ion conductive layer when using an electrochromic layer having a solid acid catalytic activity. As an example of the electrochromic device of the present invention, an example shown in FIG. 1 can be given. This device has a stripe member 1 1 in which a transparent conductive film 32 on a transparent substrate 31 and conductive fine particles formed on the transparent conductive film 32 are bound with a binder. (Or a dot member 11, 1) is provided with a counter electrode in which it is uniformly arranged at appropriate intervals. C A front view of this counter electrode is shown in FIG. 2 or FIG. 2 and 3, reference numeral 2 'denotes a transparent conductive film on a transparent substrate.

On the other side opposite to the counter electrode, a color electrode formed by forming a transparent color conductive film 36 on a transparent substrate 37 and a reduction color (or oxidation color) electoral port chromic film 35 is formed. Is formed. The gap between the two is filled with an electrolyte 34, the periphery is sealed with a sealing material 38, and the transparent conductive film (32, 36) is connected to a power supply 39 via a lead wire via a bus 40. Have been.

In the manufacture of the electrochromic device of the present invention, the method of making the electrochromic color-forming electrode on which the electrochromic film is disposed and the counter electrode facing each other and the method of arranging the busper are not particularly limited. Various methods are possible depending on the form.

[Industrial applicability]

The electrolyte of the present invention can be used as an electrolyte for electrochemical devices such as all-solid-state secondary batteries, wet solar cells, electric double-layer capacitors, electrolytic capacitors, and electrochromic devices. The improved adhesion to the electrodes and the high ionic conductivity, mechanical strength, and stability over time make it possible to easily manufacture higher-performance electrochemical devices. It can be suitably used as an electrolyte for secondary batteries, high-energy batteries, and the like. Even when used in electrochemical devices, it has features such as no problems such as liquid leakage and excellent flame retardancy and durability.

In addition, the electroporous chromic element of the present invention can significantly improve the durability of the electrochromic element by including a predetermined amount of a basic amine compound in the electrolyte layer. It was possible to suppress a decrease in transparency of the chromic element during use over time.

Further, in the electoric chromic element of the present invention, since it is not affected by the film physical properties of the electoral chromic layer, it is possible to suppress a change in the color responsiveness in the heat resistance test. Therefore, the electoric chromic element of the present invention is required to have durability. It can be used for various purposes such as windows and partitions of buildings and vehicles, various dimming devices, and furthermore, for example, character display devices, anti-glare mirrors, and decorative devices.

[Best Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1

(1) Preparation of solid electrolyte film

Poly (hexa fluoroalkyl propylene to vinylidene fluoride I) (trade name: Atofuina 'Japan Ltd. K YNAR 275 1) 2 g, pyridine 50 mg and L i BF ₄ 0. 3 g: the, Toryechiru phosphate 2 g and Aseton 6 g) to obtain a uniform solution, and after cooling to room temperature, apply it on a glass substrate by a dough-blade method, then heat and dry to evaporate the acetone in the solution, and make it 200 μm thick. A film-like solid electrolyte was obtained.

As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 48.8% by mass of triethyl phosphate.

The solid electrolyte is easily peeled off from the glass substrate, it can be handled, the tensile elastic modulus was ^{^{3 X 10 β Ν / πι 2}} .

The solid electrolyte was measured ionic conductivity at complex Inpidansu method to obtain a good value of 1 X 10- ⁴ SZ cm.

(2) Durability test

This film-shaped solid electrolyte was placed in an oven at 100 ° C, and after 1000 hours, the film was dissolved in dimethyl sulfoxide d ₆ ((CD ₃ ) ₂ S 0; heavy DMS 0) and subjected to NMR spectroscopy. Torr was measured and the hydrolysis of the residual solvent was observed. The results are shown in Table 1. From Table 1, it is clear that no hydrolysis of the solvent contained in the solid electrolyte occurs and the durability is excellent. · Example 2

Poly (vinylidene fluoride hexafluoropropylene) (trade name: Atofina 'KYNAR 2801 manufactured by Japan') 2 g, 4, 4 '-Viviridyl 50 mg and lithium trifluoromethanesulfonimid (LiTFS I) 0. 5 g was dissolved by heating in 8 g of triethyl phosphate to obtain a uniform solution. After cooling to room temperature, the solution was coated on a glass substrate by the doctor plate method, and then dried by heating to obtain a solution of phosphoric acid in the solution. chill evaporated 50 wt%, 200〃M of ¹ H- NMR scan Bae spectrum measurement of a uniform film-like solid electrolyte was obtained _c to give a film of thickness results, triethyl phosphate 46.8 mass in the film %.

This solid electrolyte was easily separated from the glass substrate and could be handled, and the tensile elastic modulus was 4 × 10 ⁶ N / m ² .

Also the solid electrolyte was obtained by complex Inpi one dance method Ion conductivity measured Toko filtration, good numerical values of 2 X 10- ⁴ SZcm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Example 3

Poly (vinylidene fluoride-hexafluoropropylene) (trade name: Atofina-Japan, mixture of KYNAR2751 and 2801, mixing ratio 1: 1) 2 g, isoquinoline 5 Omg and LiTFS I 0.5 g, phosphorus Heat and dissolve in 8 g of Triethyl acid to obtain a uniform solution, cool to room temperature, apply it on a glass substrate by the doctor blade method, and then heat and dry to evaporate the Triethyl phosphate in the solution. A film-like solid electrolyte having a uniform thickness was obtained.

As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 47.5% by mass of triethyl phosphate.

This solid electrolyte was easily peeled off from the glass substrate and could be handled, and the tensile elastic modulus was 3 × 10 ^fiN / m ² .

When the ionic conductivity of this solid electrolyte was measured by the complex impedance method, 1. obtain good numerical value of 8 x 10_ ⁴ SZcm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Example 4

Poly (full Uz fluoride one to hexa Fluorochemicals propylene): - (trade name Atofuina Japan Ltd. K YNAR 275 1) 2 gヽisoquinoline 50 mg and _{_{L i S 0 3 CF 3 0.}} 3 g, Toryechiru phosphoric acid 8 g After heating and dissolving in a solution, a uniform solution was obtained, and after cooling to room temperature, the solution was coated on a glass substrate by a doctor blade method, and then dried by heating to evaporate the triethyl phosphate in the solution. A uniform film-like solid electrolyte was obtained. This solid electrolyte was easily separated from the glass substrate and could be handled, and the tensile modulus was 3 × 10 ⁶ N / m ² .

As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 45.3% by mass of triethyl phosphate.

The solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of 1 X 10- ⁴ SZ cm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Example 5

Poly (full Uz fluoride hexa fluoroalkyl propylene to single) (trade name: Atofuina - Japan Ltd. K YNAR 2751) 2 g, 4 , 4 5 - Bibirijiru 50 mg and _{_{L i SO 3 CF 3 0. 3}} g of phosphoric acid Toryechiru 8 g to obtain a uniform solution.After cooling to room temperature, apply the solution on a glass substrate by the doctor blade method, then heat and dry to evaporate triethyl phosphate in the solution. A solid electrolyte in the form of a film was obtained. This solid electrolyte was easily peeled off from the glass substrate and could be handled, and the tensile modulus was 5 × 10 ^fiN / m ² . As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 40.5% by mass of triethyl phosphate.

When this solid electrolyte was measured for ion conductivity by the complex impedance method, a good value of 8 × 10 ⁵ S / cm was obtained.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Example 6

Poly '(full Uz fluoride one to hexa fluorosilicone propylene) (trade name: Atofuina - Japan Ltd. K YNAR 275 1) 2:, 4, 4 5 - Bibirijiru 50 mg and L i TFS E 0. 5 g, phosphoric acid Heat and dissolve in 6 g of Triethyl and Triptyl Phosphate 2 to obtain a uniform solution. After cooling to room temperature, apply it to a glass substrate by a doctor blade method, and then heat dry to remove Triethyl phosphate in the solution. By mass% evaporation, a uniform film solid electrolyte having a thickness of 300 m was obtained. This solid electrolyte was easily peeled off from the glass substrate and could be handled. The tensile modulus was 1 × 10 ⁶ N / m ² , and it was confirmed that the solid electrolyte was self-supporting.

As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 48.9% by mass of triethyl phosphate and triptyl phosphate (mass ratio 1.0 / 0.9). .

The solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of 1 X 10- ⁴ S / cm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Example Ί

Poly (vinylidene fluoride hexafluoropropylene) (trade name: Atofina-Japan KYNAR275 1) 2 g, isoquinoline 50 mg and LiBF ₄ 0.3 g was heated and dissolved in a mixed solution of triethyl phosphate 8 g and propylene carbonate 3 g to obtain a uniform solution.After cooling to room temperature, the solution was coated on a glass substrate by the doctor blade method, and then heated and dried. Then, 50% by mass of the mixed solvent was evaporated to obtain a uniform solid electrolyte in the form of a film having a thickness of 200 / m. This solid electrolyte was easily peeled off from the glass substrate and could be handled. The tensile modulus was 3 × 10 ⁶ N / m ² , confirming that the solid electrolyte was self-supporting.

As a result of ¹ H-NMR spectrum measurement of the obtained film, it was found that the film contained 47.6% by mass of triethyl phosphate and propylene carbonate (mass ratio 1.0 / 0.5). .

The solid electrolyte was measured Ion conductivity at complex impedance method, 3 X 1 0 - obtain a good value of ⁴ S / cm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Comparative Example 1

Poly (hexa fluoroalkyl propylene to vinylidene fluoride I) (trade name: Atofuina Japan Ltd. K YNAR 2 7 5 1) and 2 skill] a ^ 16 ₄ 0. 3 g, the phosphoric acid Toryechi le 2 g and acetone 6 g After heating and dissolving, a uniform solution was obtained. After cooling to room temperature, the solution was coated on a glass substrate by a single-blade method, and then heated and dried to evaporate acetone in the solution. A film-like solid electrolyte having a uniform thickness was obtained. This solid electrolyte was easily separated from the glass substrate and could be handled, and the tensile modulus was 3 ^× 10 ^fi N / m ² .

The solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of ^{1 X 1 0- 4 S / cm} .

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. As is clear from Table 1, the amount of the hydrolyzate of the solvent contained in the film-shaped solid electrolyte of Comparative Example 1 was large, and the durability was lower than that of Example 1. Comparative Example 2

Poly (vinylidene fluoride-hexafluoropropylene) (Product name: KYNAR 280 1 manufactured by Atofina-Japan) 2 g and Li TFS I O. 5 g are heated and dissolved in 8 g of triethyl phosphate, and the mixture is uniformly mixed. A solution was obtained, cooled to room temperature, coated on a glass substrate by a doctor blade method, and then dried by heating to evaporate 50% by mass of triethyl phosphate in the solution. A solid electrolyte was obtained. This solid electrolyte was easily peeled off from the glass substrate and could be handled. The tensile elastic modulus was 4 × 10 ^eN / m ² , confirming that the solid electrolyte was self-supporting.

Also the solid electrolyte was obtained Toko filtrate was measured Ion conductivity at complex impedance method, a good value of 2 X 10- ⁴ S / cm.

Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. As is clear from Table 1, the amount of the hydrolyzate of the solvent contained in the film-form solid electrolyte of Comparative Example 1 was large, and the durability was inferior to that of Example 1. table 1

Overview of solvent hydrolysis

Example 1 No change No change

Example 2 'No change No change

Example 3 No change No change

Example 4 No change No change

Example 5 No change No change

Example 6 No change No change

Example なし No change No change

Comparative Example 1 Many Yellowing

Comparative Example 2 Many Yellowing Example 8

(1) Fabrication of electoric chromic electrode

Tungsten oxide was evaporated to a thickness of 500 nm on 1TO glass of 10 cm × 100111 to produce an elect-opening chromic electrode.

(2) Preparation of counter electrode substrate

Activated carbon powder (product name “YP17”, manufactured by Kuraray Co., Ltd., surface area: 1500 m ² / g) 8 g, Graphite (product name “USSP”, manufactured by Nippon Graphite Trading Co., Ltd.) 4 g, and Recon varnish (trade name “7931”, manufactured by Okitsumo Co., Ltd.) 2 25 g of butyl cellosolve was added to 6.7 g and mixed to prepare an activated carbon paste. The activated carbon paste was printed as a stripe member on a lO cmx l O cm ITO glass using a screen equidistantly arranged so that the stripe member of 0〃m was 20% of the total area. Then, it was heat-cured at 180 ° C. for 90 minutes to prepare a counter electrode.

(3) Preparation of ion conductive layer precursor

L i C 10 ₄ a _{l (L i C 10 4 /} GB L solution of 1 M) mo 1 / L concentration solution in § over Petit butyrolactone of 5. 0 g, 2- (5- methyl-2 A homogeneous solution was obtained by mixing 0.03 g of hydroxyphenyl) benzotriazole (TINUVIN P, manufactured by CI BA-GEIGY) and 0.03 g of triethylamine (pKa = 10.72).

(4) Fabrication of electoric chromic element

The chromic electrode of the electoral opening was opposed to the counter electrode substrate at an interval of 0.3 mm, and the periphery was sealed with epoxy resin. The electrolyte was vacuum injected into the inside, and the injection port was sealed with epoxy resin. Next, a lead wire was connected to each of the electrochromic electrode and the counter electrode substrate to prepare a device. The performance evaluation of the obtained device was evaluated based on the following test.

(5) Evaluation of color erasing response

The change in luminous transmittance (Tv) when the electoric chromic element was colored or erased was measured. Tv was measured with a luminosity transmittance meter MODEL 304 manufactured by Asahi Spectroscopy. At the time of coloring, a current of 20 mA (regulated voltage: 1.5 V) was passed so that the chromic electrode on the electoral port side was the negative electrode and the counter electrode side was the positive electrode. When Tv reached 20%, the mode was switched to the decoloring mode, and a current of 20 mA (regulated voltage: 1.0 V) was applied so that the chromic electrode on the electoral port was positive and the opposite electrode was negative. The electrochromic device was left at 80 ° C. for 1,000 hours, but the transparency of the device was not changed. In addition, as a result of evaluating the color erasing response, the color erasing response was not changed at all. Example 9

(1) Fabrication of electoric chromic electrode

Tungsten oxide was vapor-deposited on a 10 cm × 10 cm ITO glass to a thickness of 500 nm to fabricate an electoc-chromic electrode.

(2) Preparation of counter electrode substrate

Activated carbon powder (trade name “YP 17”, manufactured by Kuraray Co., Ltd., surface area 150 OmVg) 8 g, Graphite (trade name “US SP”, manufactured by Nippon Graphite Shoji Co., Ltd.) 4 g Activated carbon paste was prepared by adding and mixing 25 g of butylcellosolve to 26.7 g. Then, a stripe member with a stripe width of 500 m and a height of 100 m comprised 20% of the total area. Using a screen placed at equal intervals so as to obtain the above, the above-mentioned activated carbon paste was printed as a stripe member on a 10 cm x 10 cm IT0 glass, and then heat-hardened at 180 ° C for 90 minutes. A counter electrode was produced.

(3) Preparation of ion conductive layer precursor

L i BF ₄ and (a 1 M L i BF ₄ / PC solution) solution in propylene carbonate at a concentration of l mo l / L 4. O: , main butoxy polyethylene glycol monomethyl drink evening acrylate (Shin-Nakamura Chemical Co. Stock Company M 40 GN [Number of oxyethylene units 4]) 1.0 g, Polyethylene glycol dimethyl acrylate (Shin-Nakamura Chemical Co., Ltd. 4G [Number of oxyethylene units 4]) 0.02 g , 1- (4-Isopropylphenyl) 1-2-hydroxy_2-methylpropane-11-0.02 g, 2- (5_methyl_2-hydroxyphenyl) benzotriazole And 0.06 g of pyridine (K a = 5.42) were mixed with each other to obtain a homogeneous solution.

(4) Fabrication of electoric chromic element

The electrochromic coloring electrode was opposed to the counter electrode substrate at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin. The electrolyte was vacuum-injected into the inside, the inlet was sealed with epoxy resin, and the electrolyte was gelled by irradiating with a fluorescent lamp overnight. Next, a lead wire was connected to each of the electorifice chromic electrode and that of the counter electrode substrate, thereby producing a device. The performance of the obtained device was evaluated based on the following test.

(5) Evaluation of color erasing response

The change in luminous transmittance (Tv) when the electoric chromic element was colored or erased was measured. Tv was measured using a luminous transmittance meter MODEL 304 manufactured by Asahi Spectroscopy o

At the time of coloring, a current of 20 mA (regulated voltage: 1.5 V) was passed so that the electoric chromic electrode side was the negative electrode and the counter electrode side was the positive electrode. When Tv reached 20%, the mode was switched to the decoloring mode, and a current of 20 mA (regulated voltage: 1.0 V) was applied so that the chromic electrode on the electoral port was positive and the opposite electrode was negative. When the electrochromic device was left at 80 ° C. for 1000 hours, the transparency of the device was not changed. In addition, as a result of evaluating the color erasing response, the color erasing response was not changed at all. Example 10

(1) Fabrication of chromic electrode for electoral opening

Oxidized tungsten was vapor-deposited to a thickness of 500 nm on I O cmx I O cm I T0 glass to produce an electrochromic coloring electrode.

(2) Preparation of counter electrode substrate

On a 10 cm × 10 cm Ito glass, an iridium oxide was deposited to a thickness of 5000 A to produce a counter electrode substrate.

(3) Preparation of ion conductive layer precursor L i BF ₄ was dissolved in § one Puchiroraku tons at a concentration of lmo 1 / L solution (1 M of L i BF ₄ / GB L solution) 4. 0 g, main butoxy polyethylene glycol monomethyl evening acrylate (Shin Nakamura Chemical M40 GN manufactured by Kogyo Co., Ltd. [Number of oxyethylene units 4]) 1.0 g, polyethylene glycol dimethacrylate (4G manufactured by Shin-Nakamura Chemical Co., Ltd. [Number of oxyethylene units 4]) 0 .02 g, 1— (4-Isopropylphenyl) 1-2-hydroxy-2-methylpropane-1-one 0.02 2— (5-Methyl-12-hydroxyphenyl) benzotriazole '(CI BA — TINUVIN P) 0.03: GE I GY and 0.005 g of pyridine were mixed to obtain a homogeneous solution.

(4) Fabrication of electoric chromic element

The electrochromic coloring electrode and the counter electrode substrate were opposed to each other at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin. The electrolyte was vacuum-injected into the inside, the inlet was sealed with epoxy resin, and the electrolyte was gelled by irradiating with a fluorescent lamp overnight. Next, a lead wire was connected to each of the electrochromic electrode and the counter electrode substrate to prepare a device. The performance of the obtained device was evaluated based on the following test.

(5) Evaluation of color erasing response

The change in luminous transmittance (Tv) when the electoric chromic element was colored or erased was measured. Tv is measured with a luminous transmittance meter MODEL 304 manufactured by Asahi Spectroscopy.

At the time of coloring, a current of 20 mA (regulated voltage: 1.5 V) was passed so that the electoric chromic electrode side was the negative electrode and the counter electrode side was the positive electrode. When Tv reaches 20%, the mode shifts to the decoloring mode, and a current of 20 mA (regulated voltage: 1.0 V) is applied so that the chromic color developing electrode side is positive and the opposite electrode side is negative. did. When the electrochromic device was left at 80 ° C. for 1000 hours, the transparency of the device did not change. In addition, as a result of evaluating the color erasing response, the color erasing response was not changed at all. Comparative Example 3

(1) Preparation of electoric chromic electrode

Oxidized tungsten was vapor-deposited on 10 cm × 100111 1TO glass to a thickness of 500 nm to produce an elect-port chromic color electrode.

(2) Preparation of counter electrode substrate

Activated carbon powder (trade name “YP 17”, manufactured by Kuraray Co., Ltd., surface area 150 OmVg) 8 g, graphite (trade name “USSP”, manufactured by Nippon Graphite Shoji Co., Ltd.) 4 g Activated carbon paste was prepared by adding and mixing 25 g of butyl cellosolve to 26.7 g, and then the stripe member with a stripe width of 500 im and a height of 100 m was made up to 20% of the total area. Using a screen placed at equal intervals, the above-mentioned activated carbon paste was printed as a stripe member on I O cm x I O cm ITO glass, and then heat-hardened at 180 ° C for 90 minutes, and the counter electrode was Produced.

(3) Preparation of electrolyte

L i BF ₄ / GB L solution of 1 M 5. 0 g, and 2- (5-methyl-2-hydrate Rokishifueniru) Pen zone triazole (CIBA- GE I GY Inc. TINUVIN P) by mixing 0. 03 g A homogeneous solution was obtained.

(4) Fabrication of electoric chromic element

The electrochromic coloring electrode and the counter electrode substrate were opposed to each other at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin. The electrolyte was vacuum injected into the inside, and the injection port was sealed with epoxy resin. Next, a lead wire was connected to each of the electorifice chromic electrode and the counter electrode substrate to prepare a device. The performance evaluation of the obtained device was evaluated based on the following test.

(5) Evaluation of color erasing response

The change in luminous transmittance (Tv) when the electoric chromic element was colored or erased was measured. Tv was measured with a luminous transmittance meter MODEL 304 manufactured by Asahi Spectroscopy.

At the time of coloring, a current of 20 mA (regulated voltage: 1.5 V) was passed so that the chromic color developing electrode side became the negative electrode and the counter electrode side became the positive electrode. Tv reaches 20% When the voltage reached, the mode was changed to the decoloring mode, and a current of 20 mA (regulated voltage: 1.0 V) was passed so that the chromic color developing electrode side became the positive electrode and the counter electrode side became the negative electrode. As a result of leaving the electrochromic device at 800 ° C. for 100 hours, the ion conductive layer was hydrolyzed and the transparency was lowered. In addition, as a result of evaluating the coloring / decoloring responsiveness, the erasing response was reduced.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing one embodiment of the electrochromic device of the present invention. FIG. 2 is an example of a front view of a counter electrode.

FIG. 3 is an example of a front view of the counter electrode.

Claims

The scope of the claims

1. An electrolyte comprising a supporting electrolyte, an organic solvent and a basic amine compound.

2. An electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound in a polymer matrix.

3. The electrolyte according to claim 2, wherein the polymer matrix is a polyvinylidene fluoride-based polymer compound.

4. The electrolyte according to claim 1 or 2, wherein the basic amine compound is a tertiary amine.

5. The electrolyte according to claim 1, wherein the content of the basic amine compound is 1 mass ppm to 1000 mass ppm with respect to the mass of the electrolyte.

6. The electrolyte according to claim 1, wherein the organic solvent is a phosphate compound or a solvent containing a phosphate compound.

7. An electrochromic element in which an electrolyte layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer, and An electoric chromic element, wherein the electrolyte contains a basic amine compound.

8. The elect-mouth chromic device according to claim 7, wherein the basic amine compound is a tertiary amine.

9. The electoral chromic device according to claim 7, wherein the electrolyte is an electrolyte containing a supporting electrolyte, an organic solvent and a basic amine compound.

10. The electrochromic according to claim 7, wherein the electrolyte is an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound in a polymer matrix. element.

11. The electrochromic device according to claim 10, wherein the polymer matrix is a polyvinylidene fluoride-based polymer compound.

1 2. The content of the basic amine compound is 1 mass p ρ π! The electrochromic device according to claim 7, 9 or 10, wherein the electrochromic element has a mass of 1100000 ppm.

13. The electoric chromic device according to claim 9 or 10, wherein the organic solvent is a phosphate compound or a solvent containing a phosphate compound.

14. The electrochromic device according to claim 7, wherein the electrochromic layer is made of tungsten oxide.