WO2003003110A1 - Element electrochromique - Google Patents

Element electrochromique Download PDF

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Publication number
WO2003003110A1
WO2003003110A1 PCT/JP2002/006466 JP0206466W WO03003110A1 WO 2003003110 A1 WO2003003110 A1 WO 2003003110A1 JP 0206466 W JP0206466 W JP 0206466W WO 03003110 A1 WO03003110 A1 WO 03003110A1
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Prior art keywords
conductive
ion
group
substrate
electrochromic
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PCT/JP2002/006466
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English (en)
Japanese (ja)
Inventor
Takaya Kubo
Masaki Minami
Yoshinori Nishikitani
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Nippon Oil Corporation
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Publication of WO2003003110A1 publication Critical patent/WO2003003110A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte

Definitions

  • the present invention relates to an electrochromic device having a novel configuration. [Background technology]
  • a transparent conductive substrate a transparent substrate with a transparent conductive film
  • an oxidative coloring type or a reducing coloring type
  • electrolyte an electrolyte
  • an electrolyte containing an erotic chromic compound and an element in which a counter electrode substrate is sequentially provided.
  • the present invention has been made in view of such a situation, and it is not necessary to dispose a spacer material such as beads in a cell in order to produce a cell having a uniform electrode spacing. It is intended to provide an element.
  • the present invention is an electrochromic element in which an ion conductive layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electoric aperture chromic layer, The layer contains at least one ion selected from the group consisting of (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) a room temperature molten salt and a solvent in a polyvinylidene fluoride-based polymer matrix.
  • the present invention relates to an electrochromic element, which is an ion conductive sheet containing a conductive substance.
  • the present invention relates to the electrochromic device described above, wherein a member in which conductive fine particles are bound by a binder is disposed on a conductive surface of one conductive substrate.
  • a member in which conductive fine particles are bound by a binder is disposed on a conductive surface of one conductive substrate.
  • the electrochromic element of the present invention is an electrochromic element in which an ion conductive layer is sandwiched between two transparent conductive substrates, and has an electrochromic layer on at least one of the conductive substrates.
  • the above-mentioned ion conductive layer contains at least one selected from the group consisting of (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) a room temperature molten salt and a solvent in a polyvinylidene fluoride-based polymer matrix. It is an ion conductive sheet containing at least one kind of ion conductive substance. First, the ion conductive sheet of the present invention will be described.
  • the ion-conductive sheet of the present invention comprises (a) a supporting electrolyte and a solvent, (b) a room-temperature molten salt, and (c) a room-temperature molten salt and a solvent in a polymer matrix comprising a specific polymer compound. Characterized in that it contains at least one or more ion-conductive substances selected from the group consisting of:
  • ion conductive sheet of the present invention at least one or more ion conductive substances selected from (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) a room temperature molten salt and a solvent, or Further, other components to be added as desired are held in a polymer matrix composed of a polyvinylidene fluoride-based polymer compound to form a solid state or a gel state.
  • Polyvinylidene fluoride used as a polymer matrix in the present invention examples include a homopolymer of vinylidene fluoride and a copolymer of vinylidene fluoride and another polymerizable monomer, preferably a radical polymerizable monomer.
  • Examples of other polymerizable monomers to be copolymerized with vinylidene fluoride include, specifically, hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, and acrylate. Examples include chloronitrile, vinylidene chloride, methyl acrylate, methyl acrylate, methyl methacrylate, and styrene.
  • copolymerizable monomers can be used in an amount of 1 to 5 Omo 1%, preferably 1 to 25 Mo 1 ° / 0 , based on the total amount of the monomers.
  • Hexafluoropropylene is preferably used as the copolymerizable monomer.
  • a vinylidene fluoride-hexafluoropropylene copolymer obtained by copolymerizing 1 to 25 mo 1% of hexafluoropropylene with vinylidene fluoride is preferably used as an ion conductive film having a high molecular weight matrix. be able to.
  • two or more kinds of vinylidene fluoride-hexafluoropropylene copolymers having different copolymerization ratios may be mixed and used.
  • two or more of these copolymerizable monomers can be used for copolymerization with vinylidene fluoride.
  • vinylidene fluoride 10-hexafluoropropylene + tetrafluoroethylene, vinylidene fluoride + tetrafluoroethylene + ethylene, vinylidene fluoride + tetrafluoroethylene + propylene, etc.
  • vinylidene fluoride hexafluoropropylene + tetrafluoroethylene
  • vinylidene fluoride + tetrafluoroethylene + ethylene vinylidene fluoride + tetrafluoroethylene + propylene, etc.
  • the polymer matrix one kind of a polymer compound selected from a polyvinylidene fluoride polymer compound, a polyacrylate polymer compound, a polyacrylonitrile polymer compound and a polyether polymer compound is used. These can be used in combination.
  • the mixing ratio of the polymer compound can be generally not more than 200 parts by mass with respect to 100 parts by mass of the polyvinylidene fluoride-based polymer compound.
  • the number average molecular weight of the polyvinylidene fluoride polymer compound used in the present invention is usually 100,000 to 2,000,000, and preferably 100,000 to 1,000. , 0000, 0000 can be suitably used. Next, the ion conductive substance will be described.
  • At least one ion conductive substance selected from (a) a supporting electrolyte and a solvent, (b) a room temperature molten salt, and (c) a room temperature molten salt and a solvent is used.
  • salts, acids and alkalis usually used in the field of electrochemistry or batteries can be used.
  • the salts are not particularly limited, and include, for example, inorganic ion salts such as alkali metal salts and alkaline earth metal salts; quaternary ammonium salts; cyclic quaternary ammonium salts; quaternary phosphonium salts and the like. Salts are preferred.
  • salts include halogen ions, S CN-, C 1 0 4 -, BF 4 -, C
  • halogen ions S CN-, CIOBFCFSO (CF, SO) 2 N-, (C 2 F 5 S0 2 ) 2 N-, PF e As F CH3COO CH
  • the acids are not particularly limited, and inorganic acids, organic acids, and the like can be used, and specific examples thereof include sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids.
  • the alkali is 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 generally, the supporting electrolyte is present in the solvent as an upper limit of 20 M or less, preferably 10 M or less, more preferably 5 M or less, and the lower limit is preferably Usually, it is present at 0.01 M or more, preferably at 0.05 M or more, and more preferably at 0.1 M or more.
  • the upper limit of the ion conductive sheet may be 20% by mass or less, preferably 10% by mass or less, and the lower limit may be 0.01% by mass or more, preferably 0.1% by mass or more. preferable.
  • any solvent can be used as long as it is generally used for electrochemical cells and batteries.
  • propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxetane, acetate nitrile, ⁇ -butyrolactone, sulfolane, dioxolan, dimethylformamide, dimethoxetane, tetrahydrofuran, adiponitrinore, methoxylenitritol Dimethylacetoamide, methylpyrrolidinone, dimethylsulfoxide, dioxolan, sulfolane, trimethyl phosphate, and triethyl phosphate are preferred.
  • the solvent one kind may be used alone, or two or more kinds may be used in combination.
  • the amount of the solvent used is not particularly limited, but is usually 20% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, and 98% by mass in the ion conductive sheet. Hereafter, it can be contained in an amount of preferably 95% by mass or less, more preferably 90% by mass or less.
  • the room-temperature molten salt used in the present invention will be described.
  • the room temperature molten salt in the component (b) and the component (c) is a salt composed of an ion pair that is molten at room temperature consisting of only an ion pair containing no solvent component (that is, a liquid),
  • room-temperature molten salts can be used alone, or a mixture of two or more can be used.
  • Examples of the room temperature molten salt include, for example, the following.
  • R represents an alkyl group having 2 to 20, preferably 2 to 10 carbon atoms.
  • X— is a halogen ion, S CN—, C 10 4 —, BF 4 _ , (CF a SO 2 ) 2 N-, (C 2 F 5 SO 2 ) 2 N-, PF 6- , As F 6 —, CH 3 COO, CH 3 (C 6 H 4 ) S 0 3 , and (C 2 F 5 S0 2 ) Represents an anion selected from 3 C.
  • R 1 and R 2 are each an alkyl group having 1 to 10 carbon atoms (preferably a methyl group or an ethyl group), or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 13 carbon atoms (preferably Namib Njiru group) shows a may also be the same or different
  • X- represents a counter Anion, specifically a halogen ion, S CN-, C 1 ⁇ 4 -., BF 4 -, ( CF a S 0 2) 2 N- , (C 2 F 5 SO 2) 2 N -, PF 6 -, A s F 6 -, CH 3 COO-, CH 3 (C 6 H 4) S0 3 -, ( C 2 F 5 S0 2 ) 3 C-, F (HF) 2 .
  • R1, R2, R3, and R4 each represent an alkyl group having 1 or more carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms (such as a phenyl group), or .
  • X represents a Taia two on, specifically a halogen ion, S CN-, C 10 4 - , BF 4 (CF 3 S 0 2) 2 N-, (C 2 F 5 S 0 2 ) 2 N-, PF 6- , As F 6- , CH 3 COO-, CH a (C 6 H 4 ) S0 3 _, (C 2 F 5 S0 2 ) 3 C-1 and F (HF) 2 etc.
  • room temperature molten salt usually in the ion conductive sheet 0.1 mass 0/0 or more, preferably 1 mass 0 X »or more, more preferably 1 0% by mass or more, and It can be contained in an amount of 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less.
  • the ion conductive sheet of the present invention can further contain other components.
  • Other components that can be included include ultraviolet absorbers.
  • the ultraviolet absorber that can be used is not particularly limited, but typical examples thereof include organic ultraviolet absorbers such as a compound having a benzotriazole skeleton and a compound having a benzophenone skeleton.
  • a compound represented by the following general formula (1) is preferably exemplified.
  • R 8 1 is a hydrogen atom, a halogen atom or a carbon number of 1-1 0, preferably an 1-6 alkyl group.
  • the halogen atom include fluorine, chlorine, bromine, and iodine.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, a cyclohexyl group and the like.
  • the substitution position of R 8 1 is a 4- or 5-position of the benzotriazole ring, a halogen atom and the alkyl group position to the normal position 4.
  • R 8 2 is a hydrogen atom or a carbon number of 1-1 0, preferably an 1-6 alkylene Le group.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.
  • R 8 3 is 1 to carbon atoms 1 0, preferably an alkylene group or ⁇ Rukiriden group 1-3.
  • Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • the alkylidene group include an ethylidene group and a propylidene group.
  • Specific examples of the compound represented by the general formula (1) include 3- (5-chloro-2H-benzotriazol-2-yl) -15- (1,1-dimethylethyl) -4-hydroxyxybenzene Propanoic acid, 3- (2H-benzotriazo-1-yl) -2--5- (1,1-dimethylethyl) -1,4-hydroxy-1-benzeneethanic acid, 3- (2H-benzotriazole-1--2-) ) 4-Hydroxybenzene ethanoic acid, 3-
  • Examples of the compound having a benzophenone skeleton include compounds represented by the following general formula (2)
  • R 92 , R 93 , R 95 , R 96 , R 98 , and R 99 are the same or different from each other, and are a hydroxyl group, a carbon number of 1 to 10, preferably 1 to 6 anoalkyl or alkoxy groups.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a t-butyl group, and a cyclohexyl group.
  • alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, and a butoxy group.
  • R 91 , R 94 and R 97 each represent an alkylene group or an alkylidene group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
  • the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.
  • the alkylidene group include an ethylidene group and a propylidene group.
  • pl, p2, p3, ql, q2, and q3 each independently represent an integer of 0 to 3.
  • Preferred examples of the compound having a benzophenone skeleton represented by the above general formulas (2) to (4) include 2-hydroxy-14-methoxybenzophenone-15-carboxylic acid, 2,2 ' ⁇ Dihydroxy_ 4 -Methoxybenzophenone _ 5 -Hydroxybenzoic acid, 4-(2 -Hydroxybenzoinole) 1-3 -Hydroxybenzenepropanoic acid, 2,4 -Dihydroxybenzophene Non, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-1-4-methoxybenzophenone _5-sulfonic acid, 2-hydroxy-4-n-hydroxybenzophenone, 2,2'-dihydroxy-1,4'-dimethoxybenzophenone, 2,2,4'-tetrahydroxybenzophenone, 2-hydroxy-14-methoxy-1'-carboxybenzophenone, etc. Is mentioned.
  • an ultraviolet absorber is optional, and the amount of use is not particularly limited. However, when used, 0.1% by mass or more, preferably 1% by mass or more in the ion conductive sheet. It is desirable that the content be 20% by mass or less, preferably 10% by mass or less.
  • the ion conductive sheet of the present invention is obtained by molding a mixture obtained by blending the above ion conductive substance and, if desired, an optional component such as an ultraviolet absorber in a polymer matrix component, into a sheet by a known method. Can be obtained.
  • the molding method in this case is not particularly limited, and examples thereof include extrusion molding and a method of obtaining a film in a cast state.
  • Extrusion can be carried out by a conventional method, in which a polymer matrix and an electrolytic solution are mixed, heated and melted, and then formed into a film.
  • a polymer matrix and an electrolyte solution are mixed, the viscosity is adjusted with an appropriate diluent, and the mixture is applied by a usual coater used in the casting method and dried to form a film.
  • a doctor coater, blade coater, rod coater, knife coater, Rinoku Slowno recorder, gravure coater, spray coater, curtain coater can be used, and can be used depending on the viscosity and film thickness. .
  • Ion conductive sheet Ichito in the present invention ion conductivity, usually at room temperature 1 X 1 0 one 7 S / cm or more, preferably 1 X 1 0- 6 SZc m or more, more preferably 1 X 1 0- Indicates 5 SZ cm or more.
  • the ionic conductivity can be obtained by a general method such as a complex impedance method.
  • the thickness of the ion conductive sheet is appropriately selected depending on the use of the electoric chromic element, and is not particularly limited, but the lower limit is usually ⁇ or more, preferably 10 / im or more, and the upper limit is Usually, it is 3 mm or less, preferably 1 mm or less. Further, the ion conductive sheet of the present invention desirably has autonomy. In that case, usually, 2 5 the tensile modulus at ° C is 5 X 1 0 4 N / m 2 or more, good Mashiku the 1 X 1 0 5 N / m 2 or more, most preferably 5 X 1 0 5 N / m 2 or more. The tensile modulus is a value measured by using a generally used tensile tester with a strip sample of 2 cm ⁇ 5 cm.
  • the transparent conductive substrate is usually manufactured by laminating a transparent electrode layer on a transparent substrate.
  • the transparent substrate is not particularly limited, and the material, thickness, dimensions, shape, and the like are determined according to the purpose. It can be appropriately selected.
  • colorless or colored glass, netted glass, glass block, or the like may be used, and a colorless or colored resin having transparency may be used.
  • polyester such as polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate, polystyrene, cellulose triacetate And polymethylpentene.
  • transparent in the present invention refers to having a transmittance of 10 to 100%
  • substrate in the present invention refers to a substrate having a smooth surface at room temperature. It may be flat or curved, or may be deformed by stress.
  • the transparent conductive film forming the conductive layer of the electrode is not particularly limited as long as the object of the present invention is achieved, and includes, for example, a metal thin film such as gold, silver, chromium, copper, and tungsten, and a metal oxide.
  • a conductive film; Metal oxides include, for example, tin oxide, zinc oxide, zinc oxide, and those in which a trace component is doped.
  • ITO Indium Tin Oxide
  • F TO Fluorine doped Tin Oxide
  • AZO Aluminum doped Zinc Oxide
  • the film thickness is usually from 100 to 500 / x m, preferably from 500 to 300 ⁇ m.
  • 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 Q / sq, preferably 2 to 50 ⁇ / sq. .
  • the method for forming the transparent electrode film 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 sputtering method is used. In any case, it is desirable to form the substrate at a substrate temperature of 20 to 700 ° C.
  • the electrochromic device of the present invention at least one of the conductive substrates has an electrochromic layer.
  • the material constituting the electrochromic layer in the present invention may be any of an oxidative coloring electrochromic compound and a reducing coloring electrochromic compound, and may be an inorganic compound of a metal oxide.
  • various organic electorotic chromic compounds but are not particularly limited. Specifically, a transition metal oxide such as tungsten oxide, vanadium oxide, molybdenum oxide, iridium oxide, or titanium oxide, or an oxide film containing any of these in an arbitrary ratio can be given.
  • a wet method such as a sol-gel method or an electrochemical method
  • a vacuum film forming method such as a vapor deposition method, a sputtering method, an ion plating method, or a pulse laser deposition
  • a wet method such as a sol-gel method or an electrochemical method
  • a vacuum film forming method such as a vapor deposition method, a sputtering method, an ion plating method, or a pulse laser deposition
  • examples of the organic electoric chromic compound include polythiophene, oligothiophene, polypyrrole, porifenirenvinylene, polyphenylene, polyaniline, piologen, metal phthalocyanine, pyrazoline, phenylenediamine, phenazine,
  • examples of the polymer include an electroporous chromic compound such as phenoxazine, phenothiazine, tetrathiafulvalene, and fuecopene, or a derivative thereof.
  • two or more of these compounds can be used in combination, and the film can be produced by a known method.
  • the thickness of the electrochromic layer in the present invention is appropriately selected depending on the type of the electrochromic compound and other element configurations, but is usually from 0.2 m to 2 / m, preferably from 0.3 / m. xm to about 0.6 xm is desirable.
  • At least one of the transparent conductive substrates has an electrochromic layer.
  • the conductive substrate facing the conductive substrate having the electrochromic layer includes (a) ) A form using a conductive substrate, (b) a form using a conductive substrate having another electrochromic layer,
  • the electrochromic layer is disposed on both of the transparent conductive substrates, if one electrochromic layer is an oxidizing electrochromic layer, the other is a reducing electrochromic layer. When one of the electrochromic layers is a reducing electrochromic layer, the other is an oxidizing electrochromic layer. It is preferable to use a work layer.
  • a member in which conductive fine particles are bound with a binder is disposed on the conductive surface of the conductive substrate facing the conductive substrate having the electrochromic layer.
  • these conductive fine particles usually have an electric capacity of 1 Farad Zg or more, preferably 5 Farad / g or more, more preferably 10 Purad / g or more, or 1 clone or more, preferably 5 Coulomb. / g or more, more preferably 10 clones or more.
  • Specific examples of the material constituting such fine particles include a porous carbon, an inter-force ratio material, a conductive polymer compound, and a mixture thereof.
  • the conductive fine particles of the present invention having an electric capacity of not less than 1 Farad Zg have a surface area of not less than 1 Om 2 / g, preferably 50 to 500 m 2 / g, and particularly preferably 300 to 400 Om 2 / g.
  • activated carbon and the like can be preferably exemplified, but not limited thereto.
  • Such activated carbon can be obtained, for example, by a method of carbonizing activation of palm, petroleum pitch, phenolic resin, rayon fiber, polyatarilonitrile fiber, and the like.
  • Examples of the conductive fine particles capable of storing the charge amount of one clone Zg or more of the present invention include an intercalation material, a conductive polymer compound, and the like. Particularly, the charge amount can be stored within an applied voltage of 3 V. Materials that can be used are preferred.
  • examples of the conductive polymer compound include a conductive polymer compound containing polyarynin, polythiophene, polypyrrole, 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, and is usually 500 to 0.1 / zm, preferably 200 to 0.3 ⁇ m, more preferably An average particle size in the range from 50 ⁇ m to 0.5 ⁇ m is desirable.
  • an electrochromic element having a cross section shown in FIG. 1 can be preferably mentioned.
  • This device is composed of a substrate A having a transparent conductive film 32 on a transparent substrate 31 and an electrochromic layer 33 formed on the transparent conductive film 32, and a transparent substrate 41 as a counter electrode substrate. It has a substrate B provided with a transparent conductive film 42 and an electrochromic layer 43 formed on the transparent conductive film 42. The gap between the two is filled with an ion conductive sheet 51, the periphery is sealed with a sealing material 61, and the transparent conductive films (32, 42) are connected to a power source by lead wires.
  • the method for producing the electrochromic element of the present invention is not particularly limited, but usually, it can be easily produced by laminating the substrate A, the ion conductive sheet and the substrate B, and sealing the peripheral portion appropriately.
  • the electrochromic element of the present invention has excellent properties such as improved adhesion between the ion-conductive sheet and the electrode, and high ion conductivity, mechanical strength, and stability over time. Further, the electoric chromic element of the present invention can be easily manufactured because a spacer member such as a bead is not necessarily required in the ion conductive layer, and since the ion conductive layer is in a sheet shape. And excellent appearance characteristics.
  • the electrochromic device of the present invention can be applied to various uses, and can be applied to, for example, a light control device such as a window, a partition, and a lighting device, and various display devices.
  • Propylene carbonate sulfonate solution of polyvinylidene fluoride 2 g and 1 mo 1 ZL of L i C 1 O 4 to 5 g was added to obtain a heated homogeneous solution was diluted with acetone. This film was applied onto a polytetrafluoroethylene substrate by a doctor blade method and dried by heating to obtain a uniform 50 ⁇ m-thick ion conductive sheet.
  • the electrolyte is vacuum-injected into the cell in which the beads are arranged, the injection port is sealed, and the electrolyte is cured by light or heat, etc.
  • the method of the present invention uses an ion conductive sheet, which itself has a bead-like function. The appearance was good without any problems.
  • the sheet resistance is 100/3, 30. ! Using two sheets of 11 square 1 TO glass, W0 3 and I r 0 2 was formed respectively in I TO film f sputtering of each glass base plate to prepare the W0 3 substrate and I r 0 2 substrate.
  • W0 3 substrate and I r 0 2 ion-conductive sheet was cut into 2 5 cm square between the substrate - scissors bets, was performed for 10 minutes crimped in an oven at 8 0 ° C.
  • a lead wire was taken out from the opposing substrate, and the periphery of the cell was sealed in the same manner as in Example 1 to fabricate an electoric chromic element.
  • Activated carbon powder (YP17, trade name, manufactured by Kuraray Co., Ltd., surface area: 150 Om gs, average particle size is 30 / xm) 8 g
  • Graphite ((trade name: USSP, manufactured by Nippon Graphite Trading Co., Ltd.)
  • Activated carbon paste was prepared by adding 4 g of silicon resin (trade name “RZ7703”, manufactured by Nippon Tunica Co., Ltd.) to 34.3 g and adding 24 g of butyl sesolve to prepare an activated carbon paste.
  • silicon resin trade name “RZ7703”, manufactured by Nippon Tunica Co., Ltd.
  • W0 3 substrate and I R_ ⁇ 2 substrate using beads having a particle size is 0. 3 mm is opposed to the substrate spacing is one uniform, except for the inlet section, identical to the epoxy resin (Example 1 a peripheral sealed with 5 mm width by ones) of, after injection of the internal in the electrolyte L i C 1 0 4 of profile propylene carbonate solution (1M / liter), an inlet Epoki Shi resin (the same as example 1 ). Next, a lead wire was attached to each of the substrates, and an elecroport chromic element was manufactured.
  • FIG. 1 is an example showing a cross section of an electorifice chromic element.

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Abstract

L'invention concerne un élément électrochromique comprenant une couche de conduction ionique intercalée entre deux substrats conducteurs transparents. Au moins un substrat conducteur est doté d'une couche électrochromique, la couche de conduction ionique étant formée en feuille conductrice ionique contenant, dans une matrice polymère fluorure de polyvinylidène, au moins un type de substance conductrice ionique choisie entre (a) un électrolyte support et un solvant, (b) un sel fondu à température ambiante, et (c) un sel et un solvant fondus à température ambiante, la fourniture d'un élément électrochromique ne nécessitant pas forcément une matière d'espacement, par exemple des perles disposées dans une cellule aux de fins de produire une cellule présentant un intervalle entre électrodes uniforme.
PCT/JP2002/006466 2001-06-27 2002-06-27 Element electrochromique WO2003003110A1 (fr)

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Cited By (1)

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US7300166B2 (en) 2003-03-05 2007-11-27 Electrochromix, Inc. Electrochromic mirrors and other electrooptic devices

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US7738155B2 (en) 2003-03-05 2010-06-15 Electro Chromix, Inc. Electrochromic mirrors and other electrooptic devices
US8599466B2 (en) 2003-03-05 2013-12-03 Ajjer, Llc Electrochromic mirrors and other electrooptic devices

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