KR20130013957A - Solid polymer electrolyte composition and electrochromic device using the same - Google Patents

Abstract

PURPOSE: A solid polymer electrolyte composition is provided to obtain moderate strength by easily controlling hardness thereof, to prevent the generation of waste residues, and to obtain excellent response rate. CONSTITUTION: A solid polymer electrolyte composition comprises a polymer indicated in chemical formula 1, a polymerization initiator, and metal salt. In the chemical formula 1: R1 is a C1-6 alkoxy group; R2 is hydrogen, a C1-6 alkyl group, or (-CH2-O-C(=O)C(R3)=CH2); R3 is hydrogen or a C1-6 alkyl group; and n is an integer from 2-70. The weight average molecular weight of the polymer indicated in the chemical formula 1 is 400-3,000. The electrochromic device comprises a first electrode(10), a second electrode(20), an electrochromic material(31,32), and an electrolyte which is formed by photo-curing the solid polymer electrolyte composition.

Description

Solid polymer electrolyte composition and electrochromic device using same {SOLID POLYMER ELECTROLYTE COMPOSITION AND ELECTROCHROMIC DEVICE USING THE SAME}

The present invention relates to a solid polymer electrolyte composition and an electrochromic device using the same having improved ion conductivity to secure excellent electrochromic properties.

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.

In general, as shown in FIG. 1, the electrochromic device includes transparent conductive layers 12 and 22 formed on substrates 11 and 21 and transparent to first and second electrodes 10 and 20 to which an electric field is applied. An electrochromic material layers 31 and 32 stacked on the conductive layers 12 and 22 and changed in color by an applied current, and include an electrolyte 50 for ion conduction and an encapsulant 40 for sealing the electrolyte 50. It consists of.

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

The liquid electrolyte has the advantage of good ionic conductivity, but the organic solvent is depleted due to volatilization, there is a problem of liquid leakage in the manufacturing of the device, there is a disadvantage that the organic material is easily decomposed if the speed of discoloration is slow and repeated color-bleaching.

To solve this problem, U.S. Patent No. 6,667,825 discloses a liquid electrolyte that includes an ionic liquid to improve stability and lifespan.However, an ionic liquid is used as an electrolyte in a liquid form. It was still difficult to apply to film-like processing and the like. In addition, US Pat. No. 5,872,602 discloses an electrolyte which solves the problem of depletion and decomposition of an electrolyte, including AlCl ₃ -EMICl (aluminum chloride-1-ethyl-3-methylimidazolium chloride) ionic liquid. In case of exposure to a small amount of water or oxygen, the toxic gas is released and the reactivity with the organic-inorganic compound added in a small amount in the electrolyte is very high, in particular, there is a disadvantage that easily decomposes at 150 ℃ or more. In addition, the liquid electrolyte has a disadvantage in that it is difficult to maintain product stability due to volume change by side reaction or polymerization with the device constituent materials, and thin film and film processing are impossible.

Unlike liquid electrolytes, solid electrolytes are environmentally friendly because they do not have problems such as liquid leakage, and they can be thinned and processed in the form of a film. Due to the slow ion diffusion reaction, the electrochromic reaction is delayed due to low ion conductivity.

US Patent No. 6,667,825 (Dec. 23, 2003). US Patent No. 5,872,602 (1999.02.16).

It is an object of the present invention to provide a solid polymer electrolyte which can improve ion conductivity while increasing the rate of ion diffusion reaction while maintaining the advantages of the solid electrolyte.

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

1. A solid polymer electrolyte composition comprising a polymer, a polymerization initiator, and a metal salt represented by Formula 1 below:

이며, R₃는 수소 원자 또는 탄소수 1-6의 알킬기이고, n은 2-70인 정수임).(Wherein R ₁ is an alkoxy group having 1-6 carbon atoms, R ₂ is a hydrogen atom, an alkyl group having 1-6 carbon atoms or

R ₃ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2-70.

2. In the above 1, wherein the polymer represented by Formula 1 has a weight average molecular weight of 400 to 3,000 solid polymer electrolyte composition.

3. In the above 1, R ₁ is a methoxy group solid polymer electrolyte composition.

4. In the above 1, the weight ratio of the polymer and the polymerization initiator represented by the formula (1) is 8-9.99: 0.01-2 solid polymer electrolyte composition.

5. In the above 1, the weight ratio of the polymer and the polymerization initiator represented by the formula (1) is 8.6-9: 1-1.4 solid polymer electrolyte composition.

6. In the above 1, the metal salt is an alkali metal salt solid polymer electrolyte composition.

7. In the above 1, wherein the metal salt is a solid polymer electrolyte composition comprising a concentration of cations in the metal salt is 0.5 to 1.5 mol / L.

8. Electrochromic device comprising a first electrode, a second electrode, an electrochromic material and an electrolyte formed by photocuring the solid polymer electrolyte composition of any one of 1 to 7.

9. The electrochromic device of claim 8, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

The solid polymer electrolyte composition of the present invention has a fast diffusion reaction of ions such as protons or lithium ions and thus improves ionic conductivity, thereby ensuring no response when applied to an electrochromic device.

In addition, the solid polymer electrolyte composition of the present invention has a fast polymerization reaction rate and can easily control the degree of curing, thereby imparting appropriate mechanical strength.

In addition, the solid polymer electrolyte composition of the present invention has no problem of depletion of electrolytes and leakage reactions and side reactions between device constituent materials, and devices can be fabricated on various substrates, thereby making it easy to modify the structure of devices such as thin film and film. It can be simplified.

1 is a cross-sectional view of a general electrochromic device.

The present invention relates to a solid polymer electrolyte composition and an electrochromic device using the same having improved ion conductivity to secure excellent electrochromic properties.

Hereinafter, the present invention will be described in detail.

The solid polymer electrolyte composition of the present invention is characterized in that it comprises a polymer represented by the formula (1), a polymerization initiator and a metal salt.

In the present invention, as a compound capable of forming a solid polymer electrolyte by polymerization by a polymerization initiator and a photocuring reaction, the polymer represented by the formula (1) is particularly selected and used. The polymer represented by the formula (1) contains alkoxy group having polarity at one end and functional acrylic group at the other end, so that the reaction rate is high during polymerization, the volume shrinkage and expansion is small, and the degree of curing can be easily controlled. It allows the formation of a solid polymer electrolyte endowed with mechanical strength.

[Formula 1]

이며; R₃는 수소 원자 또는 탄소수 1-6의 알킬기이다. 또한, n은 2-70인 정수이다.In which R ₁ is an alkoxy group having ₁ to 6 carbon atoms, preferably a methoxy group; R ₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or

; R ₃ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In addition, n is an integer of 2-70.

The polymer represented by the formula (1) preferably has a weight average molecular weight (Mw) of 400 to 3,000. If the weight average molecular weight is less than 400, leakage may occur due to insufficient role of the backbone of the solid electrolyte. If the weight average molecular weight is greater than 3,000, the ion conductivity may be lowered and the solubility may be lowered.

인 화합물이 바람직하다.In the polymer represented by the formula (1), R ₁ is a methoxy group, and R ₂ is

Phosphorus compounds are preferred.

As a compound capable of forming a solid polymer electrolyte by photocuring together with the polymer represented by Chemical Formula 1, a small amount of a vinyl compound may be mixed and used.

The type of vinyl compound is not particularly limited, and examples thereof include (meth) acrylonitrile, methyl (meth) acrylate, vinyl ester compound, vinyl chloride, vinylidene chloride, acrylamide, tetrafluoroethylene, vinyl acetate, and methyl vinyl. Ketone, ethylene, styrene, methyl styrene, p-methoxy styrene, p-cyano styrene, and the like. These may be used alone or in combination of two or more thereof. The vinyl compound may be used in a small amount in a range in which yellowing does not occur by a polymerization initiator.

The polymerization initiator is for improving the curing reaction efficiency of the solid polymer electrolyte composition. Examples of the polymerization initiator include an optical radical generator that generates active radicals by light irradiation and an acid generator that generates an acid. It is a compound which generates simultaneously. These can be used individually or in mixture of 2 or more types.

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

Acetophenone compounds include diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [2- (2-hydroxyethoxy ) Phenyl] propan-1-one and oligomers thereof, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one etc. are mentioned.

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

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t-butylper Oxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

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.

In addition, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2 as an optical radical generating agent '-Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxylate, benzyldimethyl ketal, titanocene compound and the like may also be used. have.

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.

In addition, as polymerization initiators, commercially available products such as Optoma (Asahi telephone company), Irgacure, OXE-01 (Shiba Corporation), Seaid SI-60L, UVI-6990 (Union Carbide Corporation), BBI-1C3, MPI -103, TPS-103, DTS-103, NAT-103, NDS-103 (Midori Chemical Co., Ltd.), etc. can also be used.

The polymer represented by the formula (1) and the polymerization initiator are preferably included in the solid polymer electrolyte composition in a weight ratio of 8-9.99: 0.01-2 (based on solids), and more preferably 8.6-9: 1-1.4. good. At this time, the weight ratio of the polymer represented by the formula (1) and the polymerization initiator is based on a total weight ratio 10. When the weight ratio does not fall within the above range, for example, when the weight ratio of the polymer represented by the formula (1) is less than 8 or the weight ratio of the polymerization initiator is more than 2, the effect of improving ion conductivity is insignificant, and the polymerization or contraction may occur in the solid polymer electrolyte. Can be. In addition, when the weight ratio of the polymer represented by the formula (1) is more than 9.99 or the weight ratio of the polymerization initiator is less than 0.01, the formation of a solid polymer electrolyte is weak, and it is difficult to impart proper mechanical strength and may cause a problem of leakage.

The metal salt is for providing metal ions to the solid polymer electrolyte composition, and is used to change the optical properties of the electrochromic material itself, such as transmittance, by changing the oxidation number of the transition metal contained in the electrochromic material by being inserted into or desorbed from the electrochromic material. Do it.

Metal salts include Li ^+, Na ^+, K ^+, and cations selected from the group consisting of Cs ⁺ and ^{F -, 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 -, 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 Alkali metal salts consisting of ionic bonds of anions selected from the group consisting of SO ₃ ^- and C ₄ F ₉ SO ₃ ^- are preferred.

In particular, when inorganic metals such as WO ₃ and NiO are used as the electrochromic materials of the electrochromic device, it is preferable to use alkali metal salts containing lithium cations such as LiClO ₄ , LiAsF ₆ , LiSbF ₆ , LiPF6 or LiBF ₄ . More preferably, it is LiPF ₆ or LiBF ₄ .

The metal salt may be used by appropriately adjusting the content according to the composition of the electrolyte composition and the type of electrochromic material without affecting other components of the solid polymer electrolyte composition. The metal salt is preferably included so that the concentration of cation in the metal salt is 0.5 to 1.5 mol / L based on the total content of the solid polymer electrolyte composition. When the cation concentration 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 low, and thus, sufficient performance as an electrolyte of the electrochromic device is difficult. In addition, when more than 1.5 mol / L dissolution in the solid polymer electrolyte composition is not well formed to form an ion-pair (ie, the ion must be dissolved after the separation of + /-must be moved In an ion pair or ion aggregation state, movement becomes impossible, resulting in a small number of free ions and a low conductivity.

The method for producing a solid polymer electrolyte using the solid polymer electrolyte composition of the present invention as described above is not particularly limited. For example, it can be produced by an in-situ polymerization reaction by photocuring in an electrode. In this case, in-situ polymerization is a method of injecting and polymerizing a solid polymer electrolyte composition between two electrodes, and is easy to handle as compared to controlling the polymerized electrolyte, which is useful in manufacturing an electrochromic device. In addition, the wetting and contact state between the solid polymer electrolyte and the electrode has a good advantage.

The polymerization conditions of the solid polymer electrolyte by photocuring are not particularly limited, and may be performed with a conventional light irradiation amount, for example, within a polymerization time of 10 minutes or less.

The electrochromic device of the present invention is characterized in that it comprises a first electrode, a second electrode, an electrochromic material and an electrolyte formed by photocuring 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. The substrate may include glass, transparent plastic (polymer), and the like, and conductive materials for forming a transparent conductive layer may include indium doped tin oxide (ITO), antimony doped tin oxide (ATO), and fluorine doped tin oxide (FTO). , Indium doped zinc oxide (IZO), ZnO, and the like. 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.

Among electrochromic materials, WO ₃ is a material that is colored by a reduction reaction, and NiO is a material that is colored by an oxidation reaction. The electrochemical mechanism in which the electrochromic color occurs in the electrochromic device including the inorganic metal oxide is described as in Scheme 1 below. 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 ⁺ ; x is any integer.

The electrochromic device configured as described above 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 and sealing the solid polymer electrolyte composition according to the present invention between the prepared first electrode and the second electrode; And (c) polymerizing the injected electrolyte composition to form a solid polymer electrolyte.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Example

Example 1

(1) solid polymer electrolyte composition

Methoxypolyethyleneglycol methacrylate having Mw of 600, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (OXE-01, Cibasa) was prepared in 8.7: A solid polymer electrolyte composition was prepared by mixing at a weight ratio of 1.3 (based on solids) and adding LiPF ₆ (Li ⁺ concentration: 1 mol / L) to the total content of the composition.

(2) 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 portion of the edges of the working electrode and the counter electrode (electrolyte inlet), an electrochromic device intermediate was prepared by bonding the UV sealant to the absence of an electrolyte. The solid polymer electrolyte composition prepared in (1) was injected into the prepared intermediate, the injection hole was sealed with a UV sealant, and then irradiated with an ultraviolet (UV) exposure machine for 1 minute to produce an electrochromic device by in-situ polymerization.

Example 2

In the same manner as in Example 1, Mw of 600 methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 9: 1 (based on solids).

Example 3

In the same manner as in Example 1, Mw of 600 methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 8.5: 1.5 (based on solids).

Example 4

In the same manner as in Example 1, Mw of methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 8.7: 1.3 (based on solids).

Example 5

In the same manner as in Example 1, Mw 350 methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 8.7: 1.3 (based on solids).

Example 6

The same procedure as in Example 1, except that methoxy polyethylene glycol methacrylate having a Mw of 3,200 and OXE-01 were used in a weight ratio of 8.7: 1.3 (based on solids).

Example 7

The same procedure as in Example 1, except that methoxy polyethylene glycol methacrylate having a Mw of 600 and OXE-01 were used in a weight ratio of 7.7: 2.3 (based on solids).

Example 8

In the same manner as in Example 1, Mw of 600 methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 9.5: 0.5 (based on solids).

Example 9

In the same manner as in Example 1, Mw of 600 methoxy polyethylene glycol methacrylate and OXE-01 was used in a weight ratio of 9.995: 0.005 (based on solids).

Comparative Example 1

The same procedure as in Example 1, except that polyethylene glycol polymer having a Mw of 600 and OXE-01 were used in a weight ratio of 8.7: 1.3 (based on solids).

Comparative Example 2

The same procedure as in Example 1, except that polyethylene glycol polymer having a Mw of 1,000 and OXE-01 was used in a weight ratio of 8.7: 1.3 (based on solids).

Comparative Example 3

The same procedure as in Example 1, except that polyethylene glycol dimethacrylate polymer having Mw of 200 and OXE-01 were used in a weight ratio of 8.7: 1.3 (based on solids).

Comparative Example 4

The same procedure as in Example 1 was carried out, except that only a liquid electrolyte in which 1M LiClO ₄ was dissolved in γ-butyrolactone (GBL) was used.

The components and contents (weight ratios) of the solid polymer electrolyte compositions prepared in Examples and Comparative Examples are shown in Table 1 below.

division polymer polymerization
Initiator Metal salt
(Li ⁺ , mol / L) Liquid
Electrolyte I Ⅱ Ⅲ Ⅳ Ⅴ VI Ⅶ OXE-01 LiPF ₆ LiClO ₄ / γ-GBL Example 1 8.7 - - - - - 1.3 One - Example 2 9 - - - - - One One - Example 3 8.5 - - - - - 1.5 One - Example 4 - 8.7 - - - - 1.3 One - Example 5 - - 8.7 - - - 1.3 One - Example 6 - - - 8.7 - - 1.3 One - Example 7 7.7 - - - - - - 2.3 One - Example 8 9.5 - - - - - - 0.5 One - Example 9 9.995 - - - - - - 0.005 One - Comparative Example 1 - - - - 8.7 - - 1.3 One - Comparative Example 2 - - - - - 8.7 - 1.3 One - Comparative Example 3 - - - - - - 8.7 0.9 - - Comparative Example 4 - - - - - - - - - 10 I: methoxy polyethylene glycol methacrylate having Mw of 600
II: methoxy polyethyleneglycol methacrylate having Mw of 1,000
III: methoxy polyethylene glycol methacrylate having Mw of 350
IV: methoxy polyethylene glycol methacrylate having Mw of 3,200
V: Polyethylene glycol polymer having Mw of 600
Ⅵ: Polyethylene glycol polymer having Mw of 1,000
폴리에틸렌: polyethyleneglycol dimethacrylate polymer having Mw of 200
OXE-01: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (Shiba Corporation)

Test Example

Physical properties of the polymer electrolyte composition and the electrochromic device prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

1.Ion Conductivity of Polymer Electrolyte

Ionic 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

Infrared spectroscopy (FT-IR spectra) was used to measure the time at which curing of the polymer electrolyte composition was completed, such as elimination of double bonds and polymerization (T) change of the polymer electrolyte, based on the following criteria: .

<Evaluation Criteria>

◎: polymerization time ≤ 60 seconds

○: 60 seconds <polymerization time ≤ 120 seconds

△: 120 seconds <polymerization time ≤ 180 seconds

×: 180 seconds <polymerization time

3. Permeability (%) when electrochromic (colored / discolored)

After the electrochromic (coloring / discoloring) test of the electrochromic device was carried out for 2 hours or more, the transmittance at 400 nm was measured. At this time, the transmittance at the time of coloring was 37% or less, and it was considered that it is so good that the difference of the transmittance | permeability at the time of coloring / coloring is large.

division Ion conductivity Polymerization time Permeability (%)
(Coloring / decoloring) Example 1 ○ ◎ 32/70 Example 2 ○ ◎ 32/68 Example 3 ○ ○ 32/71 Example 4 ○ ◎ 32/69 Example 5 ○ ○ 33/71 Example 6 △ ○ 34/72 Example 7 △ ○ 33/70 Example 8 ○ ○ 32/70 Example 9 ○ △ 35/71 Comparative Example 1 △ △ 45/60 Comparative Example 2 △ △ 43/65 Comparative Example 3 △ △ 44/70 Comparative Example 4 ○ × 40/69

As shown in Table 2, the solid polymer electrolytes of Examples 1 to 9 including the polymer represented by the formula (1), the polymerization initiator and the metal salt according to the present invention showed similar ionic conductivity as the liquid electrolyte, and the polymerization reaction according to photocuring. This facilitated and easy control of the degree of curing as well as excellent transmittance characteristics due to electrochromic. In particular, when the weight average molecular weight of the polymer represented by the formula (1) is 400-3,000, and the weight ratio of the polymer represented by the formula (1) and the polymerization initiator is 8.6-9: 1-1.4 in terms of promoting the polymerization reaction and controlling the degree of curing It was more effective.

On the other hand, Comparative Examples 1 to 3 using other types of polymers not represented by Formula 1 are The polymerization time was long and the control of the polymerization reaction was difficult, and the ionic conductivity did not reach the examples. In addition, Comparative Example 4 using the liquid electrolyte had good ion conductivity due to its inherent properties, but the polymerization time was long and poor permeability.

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 (9)

A solid polymer electrolyte composition comprising a polymer represented by Formula 1, a polymerization initiator, and a metal salt:
[Formula 1]

(Wherein R ₁ is an alkoxy group having 1-6 carbon atoms, R ₂ is a hydrogen atom, an alkyl group having 1-6 carbon atoms or

R ₃ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2-70.
The solid polymer electrolyte composition of claim 1, wherein the polymer represented by Formula 1 has a weight average molecular weight of 400 to 3,000.
The solid polymer electrolyte composition according to claim 1, wherein R ₁ is a methoxy group.
The solid polymer electrolyte composition of claim 1, wherein a weight ratio of the polymer represented by Formula 1 to the polymerization initiator is 8-9.99: 0.01-2.
The solid polymer electrolyte composition according to claim 1, wherein the weight ratio of the polymer represented by Formula 1 to the polymerization initiator is 8.6-9: 1 to 1.4.
The solid polymer electrolyte composition of 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 cation in the metal salt is 0.5 to 1.5 mol / L.
An electrochromic device comprising an electrolyte formed by photocuring a first electrode, a second electrode, an electrochromic material, and the solid polymer electrolyte composition of claim 1.
The electrochromic device of claim 8, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

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