KR101716799B1 - Gel polymer electrolyte composition and electrochromic device using the same - Google Patents

Abstract

The present invention relates to a gel polymer electrolyte composition and an electrochromic device using the gel polymer electrolyte composition, and more particularly, to a gel polymer electrolyte composition comprising a copolymer of a specific compound, an ionic liquid, a polymerization initiator and a metal salt, A gel polymer electrolyte composition which is easy to maintain the stability of the production process and product by suppressing the change and has a high response speed due to improved ionic conductivity and is easy to deform the device such as a thin film and a film form, and an electrochromic device .

Description

TECHNICAL FIELD [0001] The present invention relates to a gel polymer electrolyte composition and an electrochromic device using the gel polymer electrolyte composition.

The present invention relates to a gel polymer electrolyte composition which is capable of controlling the reaction rate and curing degree during polymerization and maintaining the stability of the production process and the product as well as being capable of thinning and processing in the form of film, without the problem of electrolyte depletion and leakage, And an electrochromic device using the same.

Elctrochromic devices are devices that change the light transmission characteristics by using the principle that the electric oxidation-reduction reaction proceeds according to the application of the electric field to change the color of the electrochromic material. This is widely used not only for display devices such as mobile phones, camcorders, notebooks, but also for automobile room mirrors and window smart windows.

1, the electrochromic device generally includes first and second electrodes 10 and 20 formed with transparent electroconductive layers 12 and 22 on a substrate 11 and 21 to which an electric field is applied, The electrochromic material layer 31 and 32 are laminated on the conductive layers 12 and 22 and are changed in color by the applied electric current. The electrolyte 50 for ion conduction and the sealing material 40 for sealing the electrolyte layer 50, .

The electrolyte 50 may be a solid electrolyte deposited on the electrochromic material layers 31 and 32 or a liquid electrolyte dispersed therein.

The solid electrolyte is excellent in terms of stability of the electrochromic device, but has a disadvantage in that it is difficult to commercialize the electrochromic device due to its low performance. The liquid electrolyte has a disadvantage in that the organic solvent is volatilized and depleted, there is a liquid leakage problem in the production of the device, the decoloration rate is low, and the organic matter is easily decomposed when the coloring-decoloring is repeated. Further, it is difficult to maintain the stability of the product due to side reaction with the element constituting material or volume change due to polymerization, and it is disadvantageous in that it can not be made thin and can not be processed in a film form.

In order to solve this problem, U.S. Patent No. 6,667,825 discloses a liquid electrolyte including an ionic liquid and improved stability and lifetime. However, since an ionic liquid is used as a liquid electrolyte, electrolyte leakage, It is still difficult to apply to film-type processing.

In addition, U.S. Patent No. 5,872,602 discloses a _{AlCl 3 -EMICI (aluminum chloride-1} -ethyl-3-methylimidazolium chloride) ionic liquid, including but the electrolyte address the depletion, a problem of electrolyte degradation is disclosed, the ionic liquid Has a disadvantage in that it reacts with a small amount of organic-inorganic compound which releases a toxic gas when exposed to a small amount of water or oxygen and is added in a small amount in the electrolyte, and is easily decomposed particularly at 150 ° C or higher.

Korean Patent No. 0729500 discloses a gel polymer electrolyte impregnated with an ionic liquid without an organic solvent. However, since the vinyl monomer used as a monomer capable of forming a gel polymer is highly reactive, the storage stability of the electrolyte is low and polymerization There is a problem of a yellowing phenomenon caused by the initiator and a decrease in the transmittance.

An object of the present invention is to provide a gel polymer electrolyte composition which has high ionic conductivity, does not contain an organic solvent, has no problem of electrolyte depletion and leakage, and has no side reaction with a constituent material.

Another object of the present invention is to provide a gel polymer electrolyte composition capable of controlling the reaction rate and degree of curing at the time of polymerization and having a small volume change to maintain the stability of the production process and the product, do.

It is another object of the present invention to provide an electrochromic device including the gel polymer electrolyte composition and having improved performance.

(I) a compound having an unsaturated bond and a carboxylic acid group in one molecule, (iii) a compound having an unsaturated bond copolymerizable with the above (i) and (ii), and (iv) A copolymer of a compound having an unsaturated bond and an epoxy group in a molecule; Ionic liquids; A polymerization initiator; And a metal salt.

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ is a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms).

2. The gel polymer electrolyte composition of claim 1, wherein the copolymer is a copolymer of Formula 2:

(Wherein X is each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and k, l, m, and n are integers representing a molar ratio).

3. In the above item 1, the copolymer comprises (i) 2-60 mol% of a compound having a tricyclodecane skeleton in one molecule, (ii) 2-70 mol% of a compound having an unsaturated bond and a carboxylic acid group in one molecule, ) 2-90% by mole of a compound having an unsaturated bond copolymerizable with the above (i) and (ii), and (iv) 5-50% by mole of a compound having an unsaturated bond and an epoxy group in one molecule, 3,000 to 40,000.

4. The gel polymer electrolyte composition according to 1 above, wherein the weight ratio (by solid content) of the copolymer, the ionic liquid and the polymerization initiator is 1.5-7: 2.5-8.5: 0.03-1.

5. The gel polymer electrolyte composition according to 4 above, wherein the weight ratio (by solid content) of the copolymer, the ionic liquid and the polymerization initiator is 4.5-5.2: 4.7-5.4: 0.03-0.3.

6. The gel polymer electrolyte composition according to 1 above, which comprises a 4- to 6-functional acrylic compound.

7. The gel polymer electrolyte composition according to 6 above, wherein the 4- to 6-functional acrylic compound is at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4)

또는

이고, R₃ 내지 R₈ 중 4개 이상이

이며; R₉ 내지 R₁₂는

이고; R₁₃은 수소 원자 또는 탄소수 1-6의 알킬기임).(Wherein R ₃ to R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,

or

, And four or more of R ₃ to R ₈

; R ₉ to R ₁₂ are

ego; And R ₁₃ is a hydrogen atom or an alkyl group having 1-6 carbon atoms).

8. In the above-mentioned 7, the 4- to 6-functional acrylic compound Wherein the gel polymer electrolyte composition is at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

9. The gel polymer electrolyte composition according to the above 8, wherein the 4- to 6-functional acrylic compound is dipentaerythritol hexaacrylate.

10. The gel polymer electrolyte composition according to claim 6, wherein the 4- to 6-functional acrylic compound is contained in a weight ratio (based on solid content) of the copolymer and 3-7: 7-3.

11. The gel polymer electrolyte composition of 1 above, wherein the ionic liquid is a compound in which an ion is combined with an ion having a cation containing at least one nitrogen atom.

12. The composition of claim 11 wherein the ionic liquid is selected from the group consisting of ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, with a selected cation from the group consisting of blood rolryum, thiazolium and ^{triazolium, F -, Cl -, Br} -, I -, NO 3 -, (CN) 2 N -, BF 4 -, ClO 4 -, RSO 3 - , RCOO ^-, PF ₆ (wherein, R is an alkyl group or a phenyl group having a carbon number of _{^{1-9) -, (CF 3)}} 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, ( ^{_{CF 3) 5 PF -, (}} CF 3) 6 P -, (CF 3 SO 3 -) 2, (CF 2 CF 2 SO 3 -) 2, (C 2 F 5 SO 2) 2 N -, (CF 3 ^{_{SO 3) 2 N -, (}} CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C - _{, (CF 3 SO 2) 3} C -, CF 3 (CF 2) 7 SO 3 -, CF 3 COO -, C 3 F 7 COO -, CF 3 SO 3 - and C ₄ F ₉ SO ₃ ^- group consisting of ≪ / RTI > wherein the anion is selected from the group consisting of anions.

13. The gel polymer electrolyte composition according to 1 above, wherein the metal salt is an alkali metal salt.

14. The gel polymer electrolyte composition according to 1 above, wherein the metal salt is contained so that the concentration of the cation of the metal salt is 0.5 to 1.5 mol / L.

15. An electrochromic device comprising a first electrode, a second electrode, an electrochromic material and an electrolyte formed by photocuring of the gel polymer electrolyte composition of any one of the above 1 to 14.

16. The electrochromic device according to 15 above, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

The gel polymer electrolyte composition of the present invention has improved ionic conductivity at a level higher than that of a liquid electrolyte, so that when applied to an electrochromic device, the electrochromic device exhibits a good response rate and secures excellent electrochromic properties.

In addition, the composition of the present invention does not contain an organic solvent and thus has no problem of electrolyte depletion and leakage, has no side reaction with the constituent materials of the device, easily controls the reaction rate and curing degree upon polymerization, And the stability of the product can be maintained.

In addition, since the composition of the present invention can be manufactured on various substrates such as plastic as well as glass, it is possible to easily deform the structure of the device by a thin film and a film form, and to simplify the process.

1 is a cross-sectional view of a general electrochromic device,
FIG. 2 is a graph showing the degree of polymerization of the gel polymer electrolyte composition according to Example 9 of the present invention, measured according to the photopolymerization time, by measuring the transmittance (T) using FT-IR.

The present invention relates to a gel polymer electrolyte composition and an electrochromic device using the gel polymer electrolyte composition.

Hereinafter, the present invention will be described in detail.

The gel polymer electrolyte composition of the present invention comprises (i) a compound represented by the following formula (1), (ii) a compound having an unsaturated bond and a carboxylic acid group in one molecule, (iii) a compound having an unsaturated bond copolymerizable with (i) , And (iv) a copolymer of a compound having an unsaturated bond and an epoxy group in one molecule; Ionic liquids; A polymerization initiator; And a metal salt.

[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ is a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms).

The copolymer is a resin capable of forming a gel polymer electrolyte by polymerization by a photo-curing reaction with a polymerization initiator. The copolymer is a resin which is copolymerized from the compounds (i) to (iv) to form a gel polymer electrolyte, Can be controlled and volume shrinkage and expansion can be prevented to give appropriate mechanical strength. Particularly, the copolymer of the compounds of (i) to (iv) has acidity on the polymer chain and exhibits an appropriate range of acidity in itself, and can exhibit excellent ionic conductivity without decreasing durability.

(I) is preferably a compound represented by the formula (1), wherein R ₁ is hydrogen or a methyl group, and R ₂ is an ethylene group, preferably a phenylthioethyl (meth) acrylate.

The compound of (ii) is a compound having an unsaturated bond and a carboxylic acid group in one molecule, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, metaconic acid and itaconic acid, and anhydrides thereof; ω-caprolactone mono (meth) acrylate, etc. Among these, acrylic acid and methacrylic acid are preferable. These may be used alone or in combination of two or more.

(Iii) is a compound having an unsaturated bond copolymerizable with the compounds (i) and (ii), and the kind thereof is not particularly limited. The unsubstituted or substituted alkyl (meth) acrylates of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- Ester compounds; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (Meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, isobonyl An unsaturated carboxylic acid ester compound containing an alicyclic substituent group such as a carboxylate; 3-ethyloxetane, 3 - ((meth) acryloyloxymethyl) oxetane, 3 - ((meth) acryloyloxymethyl) Unsaturated carboxylic acid ester compounds such as oxetane and 3 - ((meth) acryloyloxymethyl) -2-trifluoromethyloxetane; Glycol mono-saturated carboxylic acid ester compounds such as oligoethylene glycol monoalkyl (meth) acrylate; Unsaturated carboxylic acid ester compounds containing aromatic substituents such as benzyl (meth) acrylate and phenoxy (meth) acrylate; Aromatic vinyl compounds such as styrene, vinyltoluene, and? -Methylstyrene; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl propionate; (Meth) acrylonitrile, and? -Chloroacrylonitrile. Of these, aromatic vinyl compounds are preferable, and vinyl toluene is more preferable. These may be used alone or in combination of two or more.

(Iv) is a compound having an unsaturated bond and an epoxy group in one molecule, and examples thereof include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (Meth) acrylate, methylglycidyl (meth) acrylate, etc. These may be used alone or in admixture of two or more.

The molar ratio of the compounds (i) to (iv) is not particularly limited, but from the viewpoint of maintaining durability and imparting ionic conductivity, 2-60 mol%: 2-70 mol%: 2 -90 mol%: 5-50 mol%. That is, when copolymerized at this molar ratio, the polymerization reaction rate can be promoted and the degree of curing can be controlled easily, and at the same time, the effect of improving ionic conductivity can be secured.

The copolymer preferably has a weight average molecular weight (in terms of polystyrene) measured by gel permeation chromatography (GPC) of 3,000 to 40,000, more preferably 9,000 to 30,000. If the weight average molecular weight is less than 3,000, cracking may occur on the electrolyte due to the volume contraction of the electrolyte due to the bonding reaction between the copolymers. If the weight average molecular weight is more than 40,000, the polymerization reaction rate may be lowered and electrolyte leakage may occur.

In the present invention, the copolymer is preferably a copolymer of the following formula (2).

(2)

In the formulas, each X is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, k, l, m and n are integers representing molar ratios, Can be determined according to the weight average molecular weight.

The method for producing the copolymer is not particularly limited and can be produced by methods such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. Specifically, the reaction temperature and time may be appropriately adjusted depending on the kind and molar ratio of the compounds (i) to (iv), for example, polymerization may be performed at 60-130 ° C for 1-10 hours. A solvent and a polymerization initiator usually used in polymerization may be used, and a chain transfer agent for controlling molecular weight or molecular weight distribution may be used. The method of introduction during polymerization is not particularly limited.

In the present invention, a 4- to 6-functional acrylic compound may be used together with the copolymer.

The 4- to 6-functional acrylic compound is a compound capable of forming a gel polymer electrolyte by polymerization by photocuring with an ionic liquid or an ionic liquid and a polymerization initiator. This compound can further improve the ionic conductivity, It is possible to form a gel polymer electrolyte having a high reaction speed, easy control of the degree of curing, a low volume shrinkage and expansion, and an appropriate mechanical strength.

As the 4- to 6-functional acrylic compounds, (3) or (4), and they may be used alone or in combination of two or more.

(3)

[Chemical Formula 4]

또는

이고, R₃ 내지 R₈ 중 4개 이상이

이며; R₉ 내지 R₁₂는

이고; R₁₃은 수소 원자 또는 탄소수 1-6의 알킬기임).(Wherein R ₃ to R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,

or

, And four or more of R ₃ to R ₈

; R ₉ to R ₁₂ are

ego; And R ₁₃ is a hydrogen atom or an alkyl group having 1-6 carbon atoms).

As the 4- to 6-functional acrylic compounds, Ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like are more preferable, and the 5 or 6-functional acrylic-based Compounds such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, and most preferably dipentaerythritol hexaacrylate. The 5 or 6 functional acrylic compound represented by the general formula (3) has an oxyalkylene group having a polarity at the center and contains at least five functional acrylic groups at the terminals, which can further improve the ionic conductivity, It is easier.

4 to 6 functional acrylic compounds may be contained in a weight ratio (based on solid basis) of 3-7: 7-3 based on the total weight ratio of the copolymer and the 4- to 6-functional acrylic compound. If it is contained in this weight ratio, the ionic conductivity can be improved and the polymerization reaction can be promoted in the gel polymer formation, so that the gel polymer electrolyte having no volume change can be effectively formed.

A small amount of a vinyl compound can be mixed and used as a compound capable of forming a gel polymer electrolyte by photo-curing together with a 4- to 6-functional acrylic compound.

The kind of the vinyl compound is not particularly limited and includes, for example, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, methyl styrene, vinyl ester compounds, vinyl chloride, vinylidene chloride, acrylamide, tetrafluoro Ethylene, vinyl acetate, methyl vinyl ketone, ethylene, styrene, paramethoxystyrene, p-cyanostyrene, polyethylene glycol acrylate, etc. These may be used alone or in combination of two or more. The vinyl compound can be used in a small amount insofar as the yellowing by the polymerization initiator does not occur.

An ionic liquid is an ionic compound made by combining ions of a cation and an anion and is an ionic salt having a property of being present as a liquid at a temperature of 100 ° C or lower. In particular, in the present invention, the ionic liquid preferably contains at least one nitrogen atom. The free radicals generated by the nitrogen atom promote the rate of polymerization reaction to form a gel polymer electrolyte to suppress shrinkage and expansion and impart appropriate mechanical strength.

Ionic liquids are non-volatile, non-flammable, have high thermal stability and ionic conductivity, have high polarity and have unique properties to dissolve inorganic and organic metals well and maintain liquid state at wide temperature. It is a substance that has been studied as a next-generation environmentally compatible solvent.

Examples of the cation constituting the ionic liquid include ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazine, But are not limited to, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolium, thiazolium, , Triazolium, and the like.

[Chemical Formula 5]

(Wherein R ₁₄ to R ₁₉ each independently represent an alkyl group having 1 to 9 carbon atoms or a phenyl group).

The anion constituting the ionic liquid includes F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , (CN) ₂ N ^- , BF ₄ ^- , ClO ₄ ^- , RSO ₃ ^- -9 alkyl or phenyl), RCOO ^- (wherein, R is an alkyl group or a phenyl group having a carbon number of ^{_{1-9), PF 6 -, (}} CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3 ) ₄ PF ₂ ^- , (CF ₃ ) ₅ PF ^- , (CF ₃ ) ₆ P ^- , (CF ₃ SO ₃ ^- ) ₂ , (CF ₂ CF ₂ SO ₃ ^- ) ₂ , (C ₂ F ₅ SO ₂ ) _{^{2 N -, (CF 3 SO}} 3) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, ^{_{(SF 5) 3 C -,}} (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 COO -, C 3 F 7 COO -, CF 3 SO 3 -, C 4 F ₉ SO ₃ ^- , and the like.

The polymerization initiator is for improving the curing reaction efficiency of the gel polymer electrolyte composition, and includes a photo-radical generator which generates an active radical by light irradiation and an acid generator which generates an acid, At the same time. These may be used alone or in combination of two or more.

Examples of the photo radical generator include acetophenone, benzoin, benzophenone, thioxanthone and triazine compounds.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- 1-one, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one Oligomers and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- Oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- City Oak Mountain, and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trichloromethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the photo radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl- '-Bimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate and titanocene compounds.

Examples of the photopolymerization initiator include commercially available products such as Opethoma (Asahi Kogyo Co.), IGACURE (Ciba), Seid SI-60L, UVI-6990 (Union Carbide), BBI-1C3, MPI- -103, DTS-103, NAT-103, NDS-103 (Midori Chemical Industries, Ltd.).

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetic acid Triphenylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium Onium salts such as hexafluoroantimonate; Nitrobenzyl tosylate, benzoin tosylate, and the like.

It is preferable that the copolymer (or the copolymer and the 4- to 6-functional acrylic compound), the ionic liquid and the polymerization initiator are contained in the gel polymer electrolyte composition in a weight ratio (based on solid content) of 1.5-7: 2.5-8.5: 0.03-1 More preferably 1.7-7: 2.9-5.5: 0.03-0.7, most preferably 4.5-5.2: 4.7-5.4: 0.03-0.3. At this time, the total weight ratio of the copolymer, the ionic liquid and the polymerization initiator is based on 10. When the weight ratio does not fall within the above range, for example, when the weight ratio of the copolymer is less than 1.5 or the weight ratio of the ionic liquid is more than 8.5, gel polymer electrolyte formation is weak and proper mechanical strength is difficult to be imparted. Or the weight ratio of the ionic liquid is less than 2.5, the effect of improving the ionic conductivity is insignificant and the electrochromic rate may be lowered. Further, in these ranges, it is difficult to give a synergistic effect of ionic conductivity and an appropriate mechanical strength to the gel polymer electrolyte due to the combined use of the copolymer and the ionic liquid.

The metal salt is used to provide metal ions to the gel polymer electrolyte composition. The metal salt is inserted or removed in the electrochromic material to change the oxidation number of the transition metal contained in the electrochromic material, thereby changing the optical property of the electrochromic material itself .

The metal salt is preferably an alkali metal salt comprising a combination of a cation selected from the group consisting of Li ⁺ , Na ⁺ , K ^+, and Cs ⁺ and anion constituting an ionic liquid. When the anion constituting the metal salt is different from the anion constituting the ionic liquid, the solubility of the metal salt in the gel polymer electrolyte may be lowered.

In particular, when an inorganic metal such as WO ₃ or NiO is used as an electrochromic material of an electrochromic device, it is preferable to use an alkali metal salt containing a lithium cation such as LiClO ₄ , LiAsF ₆ , LiSbF ₆ , LiPF ₆ or LiBF ₄ And more preferably LiPF ₆ or LiBF ₄ .

The metal salt may be used by appropriately adjusting the content depending on the type of the ionic liquid, the composition of the electrolyte composition, and the kind of the electrochromic material, without affecting other components of the gel polymer electrolyte composition. The metal salt is preferably contained so that the concentration of the cation of the metal salt is 0.5 to 1.5 mol / L based on the gel polymer electrolyte composition. When the concentration of the cation of the metal salt is less than 0.5 mol / L, the solubility in the gel polymer electrolyte composition is good, but the number of free ions that can be conducted is small and it is difficult to exhibit sufficient performance as an electrolyte of the electrochromic device. If the concentration is more than 1.5 mol / L, dissolution of the gel polymer electrolyte composition is not performed well and ion-paring is formed. That is, after the ion is dissolved, In the case of ion pair or ion aggregation, migration is impossible and consequently the number of free ions is reduced and the conductivity is also lowered.

The method for producing the gel polymer electrolyte using the gel polymer electrolyte composition of the present invention is not particularly limited. For example, it can be produced by an in-situ polymerization reaction by photocuring in an electrode. In this case, the in-situ polymerization is a method in which the gel polymer electrolyte composition is injected between the two electrodes and then polymerized, which is easier to handle than controlling the polymerized electrolyte, which is useful in the production of an electrochromic device. In addition, there is a good advantage of wetting and contact between the gel polymer electrolyte and the electrode.

Polymerization conditions of the gel polymer electrolyte by photo-curing are not particularly limited, and can be carried out at a polymerization time of 10 minutes or less, for example, at a normal light irradiation dose.

The electrochromic device of the present invention is characterized by comprising a first electrode, a second electrode, an electrochromic material and an electrolyte formed by photocuring of the gel polymer electrolyte composition.

The first electrode and the second electrode may have a structure in which a transparent conductive layer is formed on a substrate.

The substrate and the transparent conductive layer are not particularly limited as long as they are well known in the art. Examples of the conductive material for forming the transparent conductive layer include ITO (indium doped tin oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide ), Indium doped zinc oxide (IZO), and ZnO. A transparent conductive layer can be formed on the substrate by depositing a conductive material by a known method such as sputtering, electron beam evaporation, chemical vapor deposition, or sol-gel coating.

Examples of the electrochromic material include, but are not limited to, inorganic oxides such as WO ₃ , Ir (OH) x, MoO ₃ , V ₂ O ₅ , TiO ₂ and NiO; Conductive polymers such as polypyrrole, polyaniline, polyazulene, polypyridine, polyindole, polycarbazole, polyazine, and polythiophene; Organic coloring materials such as violon, anthraquinone, phenothiazine, and the like.

The method of laminating the electrochromic material on the electrode is not particularly limited as long as the thin film can be formed at a constant height from the basal plane along the surface profile. For example, a vacuum deposition method such as sputtering can be mentioned.

Of the electrochromic materials, for example, WO ₃ is a substance that is colored by a reduction reaction, and NiO is a substance that is colored by an oxidation reaction. The electrochemical mechanism in which electrochromism occurs in an electrochromic device containing such an inorganic metal oxide is explained as shown in Scheme 1. Specifically, when a voltage is applied to the electrochromic device, the proton (H ⁺ ) or lithium ion (Li ⁺ ) contained in the electrolyte is inserted or eliminated as an electrochromic material depending on the polarity of the electric current. The change in the oxidation number of the transition metal contained in the electrochromic material changes the optical characteristic of the electrochromic material itself, for example, the transmittance (color).

[Reaction Scheme 1]

WO ₃ (transparent) + xe + xM ↔ MxWO ₃ (dark blue)

(Wherein M is a proton or an alkali metal cation such as Li ⁺ ).

The electrochromic device thus constructed may be manufactured according to a conventional method known in the art, for example, (a) preparing a first electrode and a second electrode; (b) injecting the gel polymer electrolyte composition according to the present invention between the prepared first electrode and the second electrode, and then sealing the gel polymer electrolyte composition; And (c) polymerizing the injected electrolyte composition to form a gel polymer electrolyte.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example

Preparation Example 1. Preparation of copolymer A

The atmosphere in the neck jacket reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube was replaced with nitrogen. (0.25 mole) of 2-phenylthioethyl acrylate, 12.9 g (0.15 mole) of methacrylic acid, 44 g (0.25 mole) of benzyl methacrylate, 41.3 g (0.35 mole) of vinyltoluene, 4 g of ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed, and a chain transfer agent in which 6 g of n-dodecanethiol and 24 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed was prepared. Then, 395 g of propylene glycol monomethyl ether acetate (PGMEA) was added and the temperature was raised to 90 ° C. The mixture and the chain transfer agent were dropped into the reactor through a dropping funnel over 2 hours, and after 1 hour, the mixture was heated to 110 DEG C and reacted for 8 hours to prepare copolymer A. The prepared copolymer A had a weight average molecular weight (in terms of polystyrene) of 23,000 as measured by GPC.

Preparation Example 2. Preparation of copolymer B

Neck reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube. After the inside of the reactor was replaced with nitrogen, 164 g of ethyl acetate, 126 g of n-butyl acrylate, 10 g of benzyl methacrylate, 5 g of hydroxyethyl acrylate was charged and the external temperature of the reactor was raised to 50 캜. Separately, a solution of 0.14 g of azobisisobutyronitrile (AIBN) completely dissolved in 10 g of ethyl acetate was added dropwise using a dropping funnel. The reaction was allowed to proceed for 5 hours while maintaining the external temperature of the reactor at 50 ° C. Ethyl acetate (90 g) was slowly added dropwise for 1 hour using a dropping funnel. After further stirring at 50 DEG C for 6 hours, 304 g of ethyl acetate was added and the mixture was stirred for another 2 hours to prepare copolymer B. [ The weight average molecular weight (in terms of polystyrene) of the prepared copolymer B was about 10,000 as measured by GPC.

Example  One

(1) Gel polymer electrolyte composition

(BMI-TFSI) and diethoxyacetophenone (DEAP) in a ratio of 4.9: 5: 1 were added to the copolymer A of Preparation Example 1, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide 0.1 (based on solid content), and LiBF ₄ (Li ⁺ concentration: 1 mol / L) was added to prepare a gel polymer electrolyte composition.

(2) The electrochromic device

An ITO transparent conductive layer was deposited on the glass substrate to a thickness of 150 nm, and a 200 nm thick WO ₃ electrochromic material thin film was formed thereon by a sputtering method to prepare a working electrode. Further, a counter electrode having a NiO thin film with a thickness of 300 nm was manufactured in the same manner as the working electrode. Except for a part of the rim of the working electrode and the counter electrode (electrolyte injection hole), to form an electrochromic device intermediate without electrolyte. The gel polymer electrolyte composition prepared in (1) was injected into the prepared intermediate, the injection port was sealed with a sealing material, and then irradiated with light for 1 minute in an ultraviolet (UV) exposure apparatus to prepare an electrochromic device by in-situ polymerization.

Example 2

(1) was conducted in the same manner as in Example 1 except that the copolymer A, dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl ) Imide [BMI-TFSI] and diethoxyacetophenone (DEAP) were used at a weight ratio of 2.45: 2.45: 5: 0.1.

Example 3

(69B, weight average molecular weight of 20,000 to 30,000) and the copolymer of formula (2) instead of the copolymer A in the step (1) Ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide [BMI-TFSI] and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.9: 5: 0.1.

Example 4

(1), the copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethane Sulfonylimide [BMI-TFSI] and diethoxyacetophenone (DEAP) were used at a weight ratio of 0.975: 0.975: 8: 0.05.

Example 5

(1), the copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethane Sulfonylimide [BMI-TFSI] and diethoxyacetophenone (DEAP) in a weight ratio of 2.45: 2.45: 5: 0.1.

Example 6

(1), the copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethane Sulfonylimide [BMI-TFSI] and diethoxyacetophenone (DEAP) were used in a weight ratio of 3.25: 3.25: 3: 0.5.

Example 7

(1), the copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethane Sulfonylimide [BMI-TFSI] and diethoxyacetophenone (DEAP) were used at a weight ratio of 1.3: 3.6: 5: 0.1.

Example 8

(1), copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate [HMI -PF6], and diethoxyacetophenone (DEAP) were used at a weight ratio of 3.6: 1.3: 5: 0.1.

Example 9

(1), copolymer (69B), dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate [HMI -PF6], and diethoxyacetophenone (DEAP) were used at a weight ratio of 2.45: 2.45: 5: 0.1.

Example 10

(6H), dipentaerythritol hexaacrylate (DPHA), ionic liquid trihexyl (tetradecyl) phosphonium salt compound {[(C ₆ H ₁₃ ) 3P (C ₁₄ H ₂₉ )] [Cl]} and diethoxyacetophenone (DEAP) at a weight ratio of 2.45: 2.45: 5: 0.1.

Comparative Example 1

Except that 2-hydroxyethyl methacrylate (HEMA), an ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethane) Sulfonylimide [BMI-TFIS] and diethoxyacetophenone (DEAP) in a weight ratio of 4.9: 5: 0.1.

Comparative Example 2

Except that 2-hydroxyethyl methacrylate (HEMA) and diethoxyacetophenone (DEAP) were used in a weight ratio of 9.9: 0.1 in place of the copolymer in (1).

Comparative Example  3

(1), a liquid electrolyte in which 1 M LiBF ₄ and γ-butyrolactone (GBL) were dissolved and an ionic liquid 1-butyl-3-methylimidazolium bis Imide [BMI-TFSI] was used in a weight ratio of 5: 5.

Comparative Example 4

The same procedure as in Example 1 was carried out except that only a liquid electrolyte in which 1 M LiBF ₄ and? -Butyrolactone (GBL) were dissolved was used at a ratio of 10 by weight in (1).

Comparative Example 5

Except that dipentaerythritol hexaacrylate (DPHA), ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulphonyl chloride) were used in place of copolymer A in Example 1, (BMI-TFIS) and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.9: 5: 0.1.

Comparative Example 6

(1) was replaced by the copolymer B of Production Example 2, the ionic liquid 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (BMI-TFSI) and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.9: 5: 0.1.

The composition and content (weight ratio) of the gel polymer electrolyte composition prepared in the above Examples and Comparative Examples are shown in Table 1 below.

division Public
coalescence Monomer  Ionic liquid polymerization
Initiator Metal salt
(Li ⁺ , mol / L) Liquid
Electrolyte A Ⅰ B DPHA HEMA Ⅰ Ⅱ Ⅲ DEAP LiBF ₄ LiClO ₄
/ γ-GBL Example 1 4.9 - - - - 5 - - 0.1 One - Example 2 2.45 - - 2.45 - 5 - - 0.1 One - Example 3 - 4.9 - - - 5 - - 0.1 One Example 4 - 0.975 - 0.975 - 8 - - 0.05 One - Example 5 - 2.45 - 2.45 - 5 - - 0.1 One - Example 6 - 3.25 - 3.25 - 3 - - 0.5 One - Example 7 - 1.3 - 3.6 - 5 - - 0.1 One - Example 8 - 3.6 - 1.3 - 5 - - 0.1 One - Example 9 - 2.45 - 2.45 - - 5 - 0.1 One - Example 10 - 2.45 - 2.45 - - - 5 0.1 One - Comparative Example 1 - - - - 4.9 5 - - 0.1 One - Comparative Example 2 - - - - 9.9 - - - 0.1 One - Comparative Example 3 - - - - - 5 - - - - 5 Comparative Example 4 - - - - - - - - - - 10 Comparative Example 5 - - - 4.9 - 5 - - 0.1 One - Comparative Example 6 - - 2.45 2.45 - - - - 0.1 One - Copolymer A: The copolymer of Preparation Example 1 (weight average molecular weight 20,000-30,000)
Copolymer I: 69B (weight average molecular weight 20,000-30,000)
Copolymer B: Copolymer of Preparation Example 2 (weight average molecular weight 10,000)
DPHA: dipentaerythritol hexaacrylate
HEMA: 2-hydroxyethyl methacrylate
Ionic liquid I: 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, [BMI-TFSI]
Ionic liquid II: 1-hexyl-3-methylimidazolium hexafluorophosphate, [HMI-PF6]
Ionic liquid III: trihexyl (tetradecyl) phosphonium salt compound, [(C ₆ H ₁₃ ) 3 P (C ₁₄ H ₂₉ )] [Cl]
DEAP: Diethoxyacetophenone

Test Example

The gel polymer electrolyte compositions prepared in Examples and Comparative Examples and the properties of the electrochromic devices using the same were measured by the following methods, and the results are shown in Table 2 below.

1. Ionic conductivity of gel polymer electrolyte

Ion conductivity was measured using a conductivity meter (Inolab multi 740).

<Evaluation Criteria>

⊚: Ionic conductivity <10 ^-5 S / cm

?: 10 ^-5 S / cm? Ion conductivity <5 × 10 ^-6 S / cm

Δ: 5 × 10 ^-6 S / cm ≦ ion conductivity <10 ^-6 S / cm

×: 10 ^-6 S / cm ≦ ion conductivity

2. Polymerization time

Using an infrared spectrometer (FT-IR spectrum), the time at which the curing of the polymer electrolyte composition was completed, for example, the change of the double bonds and the change of the permeability (T) of the polymer electrolyte were measured. The results of Example 9 are shown in Fig.

<Evaluation Criteria>

◎: polymerization time ≤ 60 seconds

○: 60 seconds <polymerization time ≤ 120 seconds

?: 120 seconds <polymerization time? 180 seconds

×: 180 sec <polymerization time

3. Product stability (electrolyte shrinkage or swelling, leakage)

The stability of the product was confirmed by measuring the electrochromic color of the electrochromic device (coloration 2V 20 sec / decoloration -2V 20 sec) using a response speed meter.

<Evaluation Criteria>

&Amp; cir &amp;: 1000 times &amp;num; C (very good).

○: 500 ≦ electrochromic cycle <1000 times (good).

?: The electrochromic cycle <500 times (normal).

X: No electrochromism (poor).

4. Reflectance (%) at the time of electrochromism (discoloration / discoloration)

The electrochromic (coloring / decoloring) test of the electrochromic device was conducted for 2 hours or longer, and then the reflectance at 400 nm was measured. At this time, it was considered that the reflectance at the time of coloring was 37% or less, and the greater the difference in the reflectance value at the time of coloring / coloring, the better.

division Ion conductivity Polymerization time Product stability Reflectivity (%)
(Coloring / decoloring) Example 1 ◎ ○ ◎ 33/69 Example 2 ◎ ◎ ◎ 34/68 Example 3 ◎ ○ ◎ 32/70 Example 4 ◎ △ ○ 35/68 Example 5 ◎ ◎ ◎ 28/75 Example 6 ○ ◎ ○ 33/70 Example 7 ◎ ◎ ○ 31/73 Example 8 ◎ ○ ◎ 33/70 Example 9 ○ ○ ○ 30/72 Example 10 ○ ○ ○ 37/65 Comparative Example 1 △ ○ △ 40/60 Comparative Example 2 × ◎ △ 45/55 Comparative Example 3 ○ × × 41/66 Comparative Example 4 ◎ × × 45/70 Comparative Example 5 △ ○ △ 45/60 Comparative Example 6 △ ○ △ 41/65

As shown in the above Table 2, the gel polymer electrolytes of Examples 1 to 10 including the copolymer of the compounds (i) to (iv), the ionic liquid, the polymerization initiator and the metal salt according to the present invention have ionic conductivity similar to that of the liquid electrolyte The polymerization reaction was promoted by photocuring, the degree of curing was easy to control, and the volume and the volume of the product were not changed due to shrinkage or swelling. Thus, the product and process stability were excellent and the reflectance property was excellent according to the electrochromism. As shown in Fig. 2 (Example 9), the polymerization degree and the promotion of the polymerization reaction were confirmed through the permeability of the gel polymer electrolyte according to the polymerization time. Particularly, when a hexafunctional compound is used as the 4- to 6-functional acrylic compound together with the copolymer and the weight ratio of the ionic liquid and the polymerization initiator is in the range of 1.5-7: 2.5-8.5: 0.03-1, In case of using liquid, it was more effective not only in controlling polymerization reaction and curing but also in other properties.

On the other hand, Comparative Examples 1 and 2 using a conventional acrylic monomer in place of the copolymer had a slow polymerization time, difficulty in controlling the polymerization reaction, and shrinkage and expansion due to polymerization, resulting in poor product stability. In Comparative Examples 3 and 4 using liquid electrolytes, the ionic conductivity was good due to its inherent characteristics, but the reflectivity was poor, and the product stability due to long use or breakage was not very good. In addition, Comparative Example 5 containing a copolymer using only a part of the compounds of (i) to (iv) and Comparative Example 5 containing only a 4-6 functional acrylic compound was poor in ionic conductivity and product stability, .

10: first electrode 11: substrate for first electrode
12: conductive layer for second electrode 20: second electrode
21: substrate for a second electrode 22: conductive layer for a second electrode
31: Electrochromic material layer of the first electrode
32: Electrochromic material layer of the second electrode
40: Seal material 50: Electrolyte

Claims (16)

(I) a compound having an unsaturated bond and a carboxylic acid group in one molecule, (iii) a compound having an unsaturated bond copolymerizable with the above (i) and (ii), and (iv) A copolymer of a compound having an unsaturated bond and an epoxy group;
Ionic liquids;
A polymerization initiator; And
A gel polymer electrolyte composition comprising a metal salt:
[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ is a substituted or unsubstituted alkyl or alkenyl group having 1 to 6 carbon atoms).
The gel polymer electrolyte composition of claim 1, wherein the copolymer is a copolymer of Formula 2:
(2)

(Wherein X is each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and k, l, m, and n are integers representing a molar ratio).
(Ii) 2 to 70 mol% of a compound having an unsaturated bond and a carboxylic acid group in one molecule, (iii) 2 to 60 mol% of a compound having a tricyclodecane skeleton in one molecule, (Ii) 5-90% by mole of a compound having an unsaturated bond and an epoxy group in one molecule, and having a weight average molecular weight of 3,000 to 5,000, 40,000. &Lt; / RTI &gt;
The gel polymer electrolyte composition according to claim 1, wherein the weight ratio (by solid content) of the copolymer, the ionic liquid and the polymerization initiator is 1.5-7: 2.5-8.5: 0.03-1.
The gel polymer electrolyte composition according to claim 4, wherein the weight ratio (based on solid content) of the copolymer, the ionic liquid and the polymerization initiator is 4.5-5.2: 4.7-5.4: 0.03-0.3.
The gel polymer electrolyte composition according to claim 1, comprising a 4- to 6-functional acrylic compound.
The gel polymer electrolyte composition according to claim 6, wherein the 4- to 6-functional acrylic compound is at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4)
(3)

[Chemical Formula 4]

(Wherein R ₃ to R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,

or

, And four or more of R ₃ to R ₈

; R ₉ to R ₁₂ are

ego; And R ₁₃ is a hydrogen atom or an alkyl group having 1-6 carbon atoms).
[Claim 7] The composition according to claim 7, wherein the 4- to 6-functional acrylic compound Wherein the gel polymer electrolyte composition is at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
The gel polymer electrolyte composition according to claim 8, wherein the 4- to 6-functional acrylic compound is dipentaerythritol hexaacrylate.
[Claim 7] The gel polymer electrolyte composition according to claim 6, wherein the 4- to 6-functional acrylic compound is contained in a weight ratio (based on the solid content) of the copolymer and 3-7: 7-3.
The gel polymer electrolyte composition according to claim 1, wherein the ionic liquid is a compound in which an ion is combined with an ion having a cation containing at least one nitrogen atom.
12. The process of claim 11 wherein the ionic liquid is selected from the group consisting of ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, , C ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , (CN) ₂ N ^- , BF ₄ ^- , ClO ₄ ^- , RSO ₃ ^- , RCOO ^- (wherein, R is an alkyl group or a phenyl group having a carbon number of ^{_{1-9), PF 6 -, (}} CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3 ^{_{) 5 PF -, (CF 3}} ) 6 P -, (CF 3 SO 3 -) 2, (CF 2 CF 2 SO 3 -) 2, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 3 ^{_{) 2 N -, (CF 3}} SO 2) (CF 3 CO) N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, ( ^{_{CF 3 SO 2) 3 C -}} , CF 3 (CF 2) 7 SO 3 -, CF 3 COO -, C 3 F 7 COO -, CF 3 SO 3 - and C ₄ F ₉ SO ₃ ^-, selected from the group consisting of Anions, and combinations thereof.
The gel polymer electrolyte composition according to claim 1, wherein the metal salt is an alkali metal salt.
The gel polymer electrolyte composition according to claim 1, wherein the metal salt is contained so that the concentration of the cation of the metal salt is 0.5 to 1.5 mol / L.
An electrochromic device comprising a first electrode, a second electrode, an electrochromic material, and an electrolyte formed by photocuring of the gel polymer electrolyte composition of any one of claims 1 to 14.
16. The electrochromic device according to claim 15, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

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