KR101766208B1 - Solid polymer electrolyte composition and electrochromic device using the same - Google Patents

Abstract

The present invention relates to a solid polymer electrolyte composition and an electrochromic device using the polymer polymer electrolyte composition. More particularly, the present invention relates to an electrochromic device comprising a copolymer of a specific compound, a polymerization initiator and a metal salt, And the film shape, it is possible to maintain the stability of the manufacturing process and the product, and to improve the ionic conductivity as well as to maintain the advantages of the solid form which is easy to deform the device, And to provide an electrochromic device using the solid polymer electrolyte composition.

Description

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

The present invention relates to a solid polymer electrolyte composition and an electrochromic device using the polymer electrolyte composition. The solid polymer electrolyte composition has a high polymerization reaction and an easy control of the degree of curing to maintain the stability of the production process and the stability of the product.

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, .

As the electrolyte (50), a liquid electrolyte and a solid polymer electrolyte are used.

Liquid electrolytes have the advantage of good ionic conductivity, but they are disadvantageous in that the organic solvent is volatilized and depleted, there is a liquid leakage problem in manufacturing the device, the decolorization rate is slow, and the organic matter is easily decomposed by repeated coloring-decoloring.

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. In addition, the liquid electrolyte is disadvantageous in that it is difficult to maintain the stability of the product due to side reaction with the constituent material or volume change due to polymerization, and thinning and processing in the form of a film is impossible.

Unlike liquid electrolytes, solid electrolytes are environmentally friendly because they do not have the same problems as leakage of liquid, and they can be thinned and processed in film form, making it easy to change the structure of a device in any desired form. On the other hand, There is a disadvantage in that the electrochemical reaction is delayed due to the slow ion diffusion and low ionic conductivity.

It is an object of the present invention to provide a solid polymer electrolyte capable of improving the ionic conductivity by maintaining the advantages of a solid electrolyte while accelerating an ion diffusion reaction.

Another object of the present invention is to provide a solid polymer electrolyte which is easy to control the reaction rate and degree of curing at the time of polymerization and has a small volume change, thereby enabling the production process and stability of the product to be maintained.

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

(I) a compound having a tricyclodecane skeleton in one molecule, (ii) 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 one molecule; A polymerization initiator; And a metal salt.

2. The solid polymer electrolyte composition according to 1 above, wherein the copolymer is a copolymer of the following formula:

(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 solid polymer electrolyte composition according to 1 above, wherein the weight ratio (based on solid content) of the copolymer and the polymerization initiator is 9-9.99: 1-0.01.

5. The solid polymer electrolyte composition according to 4 above, wherein the weight ratio (based on solid content) of the copolymer and the polymerization initiator is 9.8-9.95: 0.2-0.05.

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

7. The solid 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 (2) and a compound represented by the following formula (3)

또는

이고, R₁ 내지 R₆ 중 4개 이상이

이며; R₇ 내지 R₁₀은

이고; R₁₁은 수소 원자 또는 탄소수 1-6의 알킬기임).(Wherein R ₁ to R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,

or

, And four or more of R &_lt; ₁ > to R &_lt; _{6 &}

; R ₇ to R ₁₀ are

ego; And R < ₁₁ > 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 solid polymer electrolyte composition is at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

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

10. The solid polymer electrolyte composition according to 6 above, 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 solid polymer electrolyte composition according to 1 above, wherein the metal salt is an alkali metal salt.

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

13. An electrochromic device comprising a first electrode, a second electrode, an electrochromic material, and an electrolyte formed by photocuring of the solid polymer electrolyte composition of any one of the above 1-12.

14. The electrochromic device according to 13 above, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

The solid polymer electrolyte composition of the present invention has a high polymerization reaction rate and easy control of the degree of curing, so that it can impart appropriate mechanical strength and shrinkage or swelling of the volume during polymerization is small, so that it is easy to maintain the stability of the production process and the product.

In addition, the composition of the present invention improves ionic conductivity by prolonging the diffusion reaction of ions such as proton or lithium ion, so that there is no residue when applied to an electrochromic device and a satisfactory response speed can be secured.

In addition, the composition of the present invention has no problems of depletion and leakage of electrolyte, and it is possible to fabricate devices on various substrates, so that the structure of the device can be easily deformed by thinning and film form, and the process can be simplified.

1 is a cross-sectional view of a general electrochromic device,
FIG. 2 is a graph showing the degree of polymerization according to the photopolymerization time of the solid polymer electrolyte composition according to Example 5 of the present invention measured by measuring the transmittance (T) using FT-IR.

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

Hereinafter, the present invention will be described in detail.

The solid polymer electrolyte composition of the present invention is a solid polymer electrolyte composition comprising (i) a compound having a tricyclodecane skeleton in one molecule, (ii) a compound having an unsaturated bond and a carboxylic acid group in one molecule, (iii) A compound having an unsaturated bond, and (iv) a copolymer of a compound having an unsaturated bond and an epoxy group in one molecule; A polymerization initiator; And a metal salt.

The copolymer is a resin capable of forming a solid polymer electrolyte by polymerization by a polymerization initiator and a polymerization initiator. It is a resin which is copolymerized from compounds (i) to (iv) to form a solid 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.

The compound of (i) is not particularly limited as long as it is a compound having a tricyclodecane skeleton in one molecule.

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. These may be used singly 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 (1).

[Chemical Formula 1]

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 solid polymer electrolyte by polymerization by a polymerization reaction with a polymerization initiator. This compound can further improve the ionic conductivity, and has a high reaction rate during polymerization and control of the degree of curing Is easily formed and the volume shrinkage and swelling are small, so that it is possible to form a solid polymer electrolyte having appropriate mechanical strength.

Examples of the 4- to 6-functional acrylic compound include compounds represented by the following formula (2) or (3), which may be used alone or in combination of two or more.

(2)

(3)

또는

이고, R₁ 내지 R₆ 중 4개 이상이

이며; R₇ 내지 R₁₀은

이고; R₁₁은 수소 원자 또는 탄소수 1-6의 알킬기임).(Wherein R ₁ to R ₆ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,

or

, And four or more of R &_lt; ₁ > to R &_lt; _{6 &}

; R ₇ to R ₁₀ are

ego; And R < ₁₁ > 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 (2) has an oxyalkylene group having a polarity at the center and contains at least five functional acrylic groups at the terminals, thereby improving the ionic conductivity and controlling the degree of curing 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. When included in this weight ratio, the ionic conductivity is improved and the polymerization reaction is promoted in the formation of the solid polymer, so that the solid 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 solid polymer electrolyte by photocuring 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.

The polymerization initiator is for improving the curing reaction efficiency of the solid 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.

The copolymer (or the copolymer and the 4- to 6-functional acrylic compound) and the polymerization initiator are preferably contained in the solid polymer electrolyte composition in a weight ratio (based on solid content) of 9-9.99: 1-0.01, more preferably 9.4- 9.97: 0.6-0.03, and most preferably 9.8-9.95: 0.2-0.05. At this time, the total weight ratio of the copolymer 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 9 or the weight ratio of the polymerization initiator is more than 1, the effect of increasing ionic conductivity is insignificant and shrinkage or swelling may occur in the solid polymer electrolyte during polymerization. When the weight ratio of the co-polymer is more than 9.99 or the weight ratio of the polymerization initiator is less than 0.01, the formation of the solid polymer electrolyte is weak and it is difficult to give proper mechanical strength and leakage problems may occur.

The metal salt is used to provide a metal ion to the solid 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 .

Examples of the metal salt include a cation selected from the group consisting of Li ⁺ , Na ⁺ , K ^+, and Cs ⁺ and a cation selected from the group consisting of F ^- , Cl ^- , Br ^- , I ^- , NO ₃ ^- , (CN) ₂ N ^- , BF ₄ ^{- _{4 -, RSO 3 -, RCOO}} - ( wherein, R is an alkyl group or a phenyl group having a carbon number of ^{_{1-9), PF 6 -, AsF}} 6 -, SbF 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 ^- are preferable.

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 thereof depending on the composition of the electrolyte composition and the kind of the electrochromic material, without affecting other components of the solid polymer electrolyte composition. The metal salt is preferably contained so that the cation concentration of the metal salt is 0.5 to 1.5 mol / L based on the solid polymer electrolyte composition. When the concentration of the cation of the metal salt is less than 0.5 mol / L, the solubility in the solid polymer electrolyte composition is good, but the number of free ions that can be conducted is small, so that it is difficult to exhibit sufficient performance as an electrolyte of the electrochromic device. In addition, when it exceeds 1.5 mol / L, the solid polymer electrolyte composition does not dissolve well and forms ion-paring. That is, after ion dissolution, 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 solid polymer electrolyte using the solid 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 a solid polymer electrolyte composition is injected between two electrodes and then polymerized. The in-situ polymerization is easier to handle than controlling the polymerized electrolyte and is useful in the production of an electrochromic device. In addition, there is a good advantage of wetting and contact between the solid polymer electrolyte and the electrode.

Polymerization conditions of the solid 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 solid 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), and the like. , Indium doped zinc oxide (IZO), and zinc oxide (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, 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 solid polymer electrolyte composition according to the present invention between the prepared first electrode and the second electrode, and then suturing; And (c) polymerizing the injected electrolyte composition to form a solid 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 1. Copolymer A preparation

182 g of propylene glycol monomethyl ether acetate (PGMEA) was added to a neck jacket reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen gas introducing tube, and the atmosphere in the reactor was replaced with nitrogen. Thereto were added 44.0 g (0.2 mole) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical), 38.7 g (0.45 mole) of methacrylic acid, 105.6 g (0.6 mole) of benzyl methacrylate, (0.15 mol) of 2-hydroxyethyl methacrylate and 136 g of propylene glycol monomethyl ether acetate (PGMEA) were added to a solution of 3.6 g of azobisisobutyronitrile in a dropping funnel over 2 hours And the mixture was further stirred at 100 ° C for 5 hours. Subsequently, 22.5 g (0.15 mol) of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the atmosphere in the reactor, and reacted at 110 DEG C for 6 hours to prepare a copolymer A . The prepared copolymer A had a weight average molecular weight (in terms of polystyrene) measured by GPC of 20,000 to 30,000.

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 1

(1) Solid polymer electrolyte composition

Copolymer A of Preparation Example 1 and Diethoxyacetophenone (DEAP) was mixed at a weight ratio (based on solid content) of 9.95: 0.05 and LiBF ₄ (Li ⁺ concentration: 1 mol / L) was added to prepare a solid 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. Electrochromic devices were fabricated by in situ polymerization by injecting the solid polymer electrolyte composition prepared in (1), sealing the injection port with a sealant, and irradiating the prepared intermediate with an ultraviolet (UV)

Example 2

(DPHA) and diethoxyacetophenone (DEAP) in a weight ratio of 4.975: 4.975: 0.05 were used in the same manner as in Example 1, except that the copolymer A, dipentaerythritol hexaacrylate (DPHA) and diethoxyacetophenone (DEAP)

Example 3

(SPCY-1L, fire hydrant construction: weight-average molecular weight 20,000-30,000) and a copolymer of the formula (1) were used instead of the copolymer A in the step (1) Diethoxyacetophenone (DEAP) was used in a weight ratio of 9.95: 0.05.

Example 4

(SPCY-1L), dipentaerythritol hexaacrylate (DPHA) and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.975: 4.975: 0.05 in the same manner as in Example 1, Respectively.

Example  5

The copolymer (SPCY-1L), the copolymer Dipentaerythritol hexaacrylate (DPHA), and diethoxyacetophenone (DEAP) were used at a weight ratio of 4.95: 4.95: 0.1.

Example 6

The copolymer (SPCY-1L), the copolymer Dipentaerythritol hexaacrylate (DPHA), and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.75: 4.75: 0.5.

Example  7

The copolymer (SPCY-1L), the copolymer Dipentaerythritol hexaacrylate (DPHA), and diethoxyacetophenone (DEAP) were used at a weight ratio of 3.3: 6.6: 0.1.

Example 8

The copolymer (SPCY-1L), the copolymer Dipentaerythritol hexaacrylate (DPHA), and diethoxyacetophenone (DEAP) were used in a weight ratio of 6.6: 3.3: 0.1.

Comparative Example 1

The procedure of Example 1 was repeated except that the copolymer A (1) Instead, 2-hydroxyethyl methacrylate (HEMA) and diethoxyacetophenone (DEAP) were used in a weight ratio of 9.9: 0.1.

Comparative Example 2

(HEMA) and diethoxyacetophenone (DEAP) were used in a weight ratio of 9.5: 0.5 in place of the copolymer A in (1).

Comparative Example 3

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 4

Dipentaerythritol hexaacrylate (DPHA) and diethoxyacetophenone (DEAP) were used in a weight ratio of 9.9: 0.1 instead of the copolymer A in (1).

Comparative Example  5

Except that the copolymer B of Production Example 2 and diethoxyacetophenone (DEAP) were used in a weight ratio of 4.95: 4.95: 0.1 instead of the copolymer A. [

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

division Copolymer Monomer polymerization
Initiator Metal salt
(Li ⁺ , mol / L) Liquid
Electrolyte A Ⅰ B DPHA HEMA DEAP LiBF ₄ LiClO ₄ / γ-GBL Example 1 9.95 - - - - 0.05 One - Example 2 4.975 - - 4.975 - 0.05 One - Example 3 - 9.95 - - - 0.05 One - Example 4 - 4.975 - 4.975 - 0.05 One - Example 5 - 4.95 - 4.95 - 0.1 One - Example 6 - 4.75 - 4.75 - 0.5 One - Example 7 - 3.3 - 6.6 - 0.1 One - Example 8 - 6.6 - 3.3 - 0.1 One - Comparative Example 1 - - - - 9.9 0.1 One - Comparative Example 2 - - - - 9.5 0.5 One - Comparative Example 3 - - - - - - - 10 Comparative Example 4 - - - 9.9 - 0.1 One - Comparative Example 5 - - 4.95 4.95 - 0.1 One - Copolymer A: The copolymer of Preparation Example 1 (weight average molecular weight 20,000-30,000)
Copolymer I: SPCY-1L, fire hydrant construction (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
DEAP: Diethoxyacetophenone

Test Example

The 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. Polymer electrolyte ion conductivity

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

<Evaluation Criteria>

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

?: 10 ^-5 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 5 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 △ ◎ ○ 39/69 Example 8 ○ ○ ◎ 38/68 Comparative Example 1 × △ △ 40/60 Comparative Example 2 × △ △ 45/55 Comparative Example 3 ○ × × 41/66 Comparative Example 4 △ ◎ △ 45/60 Comparative Example 5 △ ○ △ 41/65

As shown in Table 2, the solid polymer electrolytes of Examples 1 to 8 including the copolymer of the compounds (i) to (iv), the polymerization initiator and the metal salt according to the present invention exhibited ion conductivity similar to that of the liquid electrolyte, The polymerization reaction was promoted according to the photocuring, the degree of curing was easily controlled, the volume and the volume change due to shrinkage or swelling were small, and thus, the product and process stability were excellent, and the reflectance characteristic according to the electrochromism was also excellent. As shown in Fig. 2 (Example 5), the degree of polymerization and the promotion of the polymerization reaction were confirmed through the permeability of the solid polymer electrolyte with the polymerization time. Particularly when 4-6 functional acrylic compounds are used together with the copolymer and the weight ratio of these and the polymerization initiator is 9-9.99: 1-0.01, it is more effective in controlling the polymerization reaction and controlling the curing degree as well as in the coloring / .

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 Example 3 using a liquid electrolyte, the ionic conductivity was good due to its inherent characteristics, but the reflectivity was not good 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 compound of (i) - (iv) and Comparative Example 4 containing only the 4-6 functional acrylic compound had poor 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 (14)

(I) a compound having a tricyclodecane skeleton in one molecule, (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 (ii) Iv) a copolymer of a compound having an unsaturated bond and an epoxy group in one molecule;
A polymerization initiator; And
(I) to (iv) are linearly repeated in the main chain in the polymer chain of the copolymer.
The solid polymer electrolyte composition according to claim 1, wherein the copolymer is a copolymer of Formula 1:
[Chemical Formula 1]

(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 solid polymer electrolyte composition according to claim 1, wherein the weight ratio (based on solid content) of the copolymer and the polymerization initiator is 9-9.99: 1-0.01.
The solid polymer electrolyte composition according to claim 4, wherein the weight ratio (based on solid content) of the copolymer and the polymerization initiator is 9.8-9.95: 0.2-0.05.
The solid polymer electrolyte composition according to claim 1, comprising a 4- to 6-functional acrylic compound.
The solid 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 (2) and a compound represented by the following formula (3)
(2)

(3)

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

or

, And four or more of R &_lt; ₁ &gt; to R &_lt; _{6 &}

; R ₇ to R ₁₀ are

ego; And R &lt; ₁₁ &gt; 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 solid polymer electrolyte composition is at least one selected from the group consisting of ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.
The solid polymer electrolyte composition according to claim 8, wherein the 4- to 6-functional acrylic compound is dipentaerythritol hexaacrylate.
[Claim 7] The solid 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.
The solid polymer electrolyte composition according to claim 1, wherein the metal salt is an alkali metal salt.
The solid 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 solid polymer electrolyte composition of any one of claims 1 to 12.
14. The electrochromic device according to claim 13, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

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