KR20140037432A - 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 same and, more specifically, to a solid polymer electrolyte composition and an electrochromic device using the same which is capable of improving durability and reliability by preventing adhesion between a discoloration layer and an opposite electrode by uniformly distributing spacers included; and maintaining uniform discoloration by adjusting a constant interval between the discoloration layer and the opposite electrode on the large-area electrochromic device.

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.

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 recent years, a liquid crystal display device in which such an electrochromic device is used has been made larger, and the size of the electrochromic device has also become larger, and it has become more and more necessary to maintain a uniform cell gap over a wide substrate. If the substrate area is large, the substrate is distorted even with a relatively small external force. Therefore, it is necessary to prevent the unevenness of the gap due to such distortion. In addition, since the thickness of the liquid crystal layer, that is, the cell gap, has been narrowed in order to improve the display responsiveness in recent years, it has also been necessary to maintain a narrow gap accurately.

Spherical or rod shaped particles of a certain size including glass, alumina, plastic and the like are dispersed and used as a spacer for maintaining such a cell gap uniform and constant in an electrochromic device. However, such a spacer was randomly dispersed and could not be uniformly dispersed, so that a narrow gap could not be accurately maintained.

The uniformity of the leak gap is slightly impaired due to enlargement of the recent display area and narrowing of the cell gap in the liquid crystal display device, which greatly affects the display performance and may degrade display quality such as display unevenness. Thus, the demand for accuracy and uniformity for cell gaps is becoming increasingly strict.

Korean Patent Publication No. 2008-22321 discloses a method of forming an electrochromic layer pattern, a method of manufacturing an electrochromic device using the method, and an electrochromic device having an electrochromic layer pattern. However, Respectively.

Korean Patent Publication No. 2008-22321

An object of the present invention is to provide a solid polymer electrolyte composition and an electrochromic device using the same, which can increase the durability and stability by preventing the adhesion between the color change layer and the counter electrode by uniformly distributing the spacers.

In addition, an object of the present invention is to provide a solid polymer electrolyte composition and an electrochromic device using the same which can maintain a uniform discoloration by constantly adjusting the distance between the discoloration layer and the counter electrode in the large area electrochromic device.

1. A solid polymer electrolyte composition comprising a spacer.

2. In the above 1, the spacer is silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, acrylic acid, methacrylic acid, polyimide, aromatic polyamide, polybenzoimidazole (polybenzoimidazole ), At least one selected from the group consisting of siloxane resin, glass, silicone and curable resin composition.

3. In the above 1, wherein the spacer is a solid polymer electrolyte composition containing 0.01 to 5% by weight relative to the total weight of the composition.

4. The solid polymer electrolyte composition according to the above 1, further comprising a polymer, a 4 to 6 functional acrylic compound, a polymerization initiator, a metal salt, and an ionic liquid.

5. In the above 4, wherein the polymer is a solid polymer electrolyte composition represented by Formula 1:

[Formula 1]

이며; R3은 수소 원자 또는 탄소수 1-6의 알킬기이며; n은 2-70의 정수임).(Wherein R1 is an alkoxy group having 1-6 carbon atoms; R2 is a hydrogen atom, an alkyl group having 1-6 carbon atoms or

; R3 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; n is an integer from 2-70.

6. In the above 4, wherein the 4 to 6 functional acrylic compound is a solid polymer electrolyte composition comprising a compound represented by the following formula (2):

(2)

또는

이고, R₁ 내지 R₆ 중 4개 이상이

임).(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 &}

being).

7. In the above 4, the ionic liquid is 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 A solid polymer electrolyte composition consisting of a combination of anions selected from.

8. In the above 4, the metal salt is selected from Li ^+, Na ^+, a cation selected from the group consisting of K ⁺ and Cs ⁺ and ^{F -, Cl -, Br -} , I -, NO 3 -, (CN) 2 N - _{^{, BF 4 -, ClO 4 -}} , RSO 3 - ( where, R is an alkyl group or a phenyl group having a carbon number of 1-9), 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 ^- alkali metal salt composed of a combination of ion anion selected from the group consisting of a solid polymer electrolyte composition.

9. In the above 4, the metal salt is a solid polymer electrolyte composition comprising a concentration of cation of the metal salt is 0.5 to 1.5 mol / L.

10. An 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 9.

11. The electrochromic device of 10 above, wherein the electrolyte is polymerized in-situ between the first and second electrodes.

The present invention can uniformly distribute the spacer to prevent adhesion between the color-changing layer and the counter electrode, thereby enhancing durability and stability.

Further, the present invention can maintain a uniform color change by controlling the interval between the color-changing layer and the counter electrode in the large-area electrochromic device to be constant.

1 schematically illustrates an embodiment of an electrochromic device manufactured using the solid polymer electrolyte composition of the present invention.

According to the present invention, the spacers are uniformly distributed, thereby preventing adhesion between the color change layer and the counter electrode, thereby increasing durability and stability, and maintaining a constant interval between the color change layer and the counter electrode in the large area electrochromic device. The present invention relates to a solid polymer electrolyte composition capable of maintaining uniform discoloration by adjusting 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 comprises a spacer.

The spacer prevents the adhesion between the coloring layer and the counter electrode in the large-area electrochromic device, and maintains a uniform color change by controlling the distance between the coloring layer and the counter electrode through the spacer to be constant.

The spacer is not particularly limited, and examples thereof include inorganic insulating materials such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, and aluminum oxynitride; Acrylic acid, methacrylic acid or derivatives thereof; Heat-resistant polymers such as polyimide, aromatic polyamide and polybenzoimidazole; Siloxane resin; Glass; silicon; A curable resin composition or the like. These may be used alone or in combination of two or more.

The shape of the spacer is not particularly limited, and examples thereof include rod-shaped and bead-shaped.

The size of the spacer is not particularly limited, and may be, for example, 1 to 150 μm.

The content of the spacer is not particularly limited within the range capable of functioning, and may include, for example, 0.01 to 5% by weight of the total weight of the solid polymer electrolyte composition. When the content of the spacer is in the above range, it is uniformly distributed in the solid polymer electrolyte composition can maintain a constant cell gap of the electrochromic device, it is possible to suppress the decrease in permeability.

The solid polymer electrolyte composition of the present invention may further include a polymer, a 4 to 6 functional acrylic compound, a polymerization initiator, and a metal salt.

The polymer has a structure represented by the following formula (1).

 [Formula 1]

이며; R3은 수소 원자 또는 탄소수 1-6의 알킬기이며; n은 2-70의 정수이다.In the formula, R 1 is an alkoxy group having 1 to 6 carbon atoms; R2 is a hydrogen atom, an alkyl group having 1-6 carbon atoms, or

; R3 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; n is an integer of 2-70.

The polymer contains an alkoxy group having a polarity at one end and a 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, so that appropriate mechanical strength is given. It allows the formation of a solid polymer electrolyte.

The polymer 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.

The polymer is not particularly limited in the range within which it can function, but may be included in the range of 30 to 65% by weight (based on solids) based on the total weight of the solid polymer electrolyte composition, preferably 35 to 60% by weight (solids) Criteria) may be included. When the content of the polymer falls within the above range, the solid polymer electrolyte may be sufficiently formed to impart appropriate mechanical strength, and the effect of improving the ionic conductivity is maximized to increase the electrochromic speed.

4- to 6-functional acrylic compound is a compound capable of forming a solid polymer electrolyte by polymerization by a polymerization initiator and photocuring, which can further improve the ionic conductivity, the reaction rate during polymerization and the control of the degree of curing It is easy and there is little volume shrinkage and expansion, which allows the formation of a solid polymer electrolyte endowed with appropriate mechanical strength.

4 to 6 functional acrylic compounds A compound represented by the following formula (2).

(2)

또는

이고, R₁ 내지 R₆ 중 4개 이상이

임).(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 &}

being).

As the 4- to 6-functional acrylic compounds, Ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like are more preferable, and more preferred are dipentaerythritol penta Acrylate, 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.

The content of the 4 to 6 functional acrylic compound is not particularly limited as long as it can function, but may be included in the range of 30 to 65% by weight (based on solids), based on the total weight of the solid polymer electrolyte composition, preferably 35 To 60% by weight (based on solids). When the content of the 4 to 6 functional acrylic compound falls within the above range, the solid polymer electrolyte may be sufficiently formed to impart the appropriate mechanical strength, and the effect of improving the ion conductivity is maximized to improve the electrochromic speed.

The polymer and the 4 to 6 functional acrylic compound may be included in a weight ratio (based on solids) of 3-7: 7-3. When included in this weight ratio, it is possible to effectively form a solid polymer electrolyte having no volume change by improving the ion conductivity and promoting the polymerization reaction when forming the solid polymer.

As a compound capable of forming a solid polymer electrolyte by photocuring together with a polymer and a 4 to 6 functional acrylic compound, a small amount of a vinyl compound can be mixed and used.

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. 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 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 content of the polymerization initiator is not particularly limited within the range capable of functioning, for example, 0.1 to 5% by weight of the total weight of the solid polymer electrolyte composition may be included, preferably 0.5 to 3% by weight. . When the content of the polymerization initiator is within the above range, the solid polymer electrolyte can be sufficiently formed to impart appropriate mechanical strength, and the degradation of electrolyte performance and the deterioration of curing performance due to residue formation can be suppressed.

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.

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 ^- (where, R is an alkyl group or a phenyl group having a carbon number of 1-9), 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 ^- 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 LiClO 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 the cation of the metal salt is 0.5 to 1.5 mol / L based on 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.

If desired, the solid polymer electrolyte composition of the present invention may further include an ionic liquid without departing from the scope of the present invention.

An ionic liquid is an ionic compound formed by ion combination of cations and anions, and is an ionic salt having the property of being present as a liquid at a temperature of 100 캜 or lower. In particular, the ionic liquid in the present invention preferably contains at least one nitrogen atom. The free radicals generated by the nitrogen atoms can promote the rate of polymerization reaction for the formation of the solid polymer electrolyte to suppress shrinkage and expansion and impart proper mechanical strength.

Ionic liquids are non-volatile, non-flammable, have high thermal stability and ionic conductivity, and because of their high polarity, they can dissolve inorganic and organometallics and have unique properties that keep them in a liquid state over a wide range of temperatures. It is a material being studied as a next generation environmentally friendly solvent.

As the cations constituting the ionic liquid, ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, and pyra represented by the formulas 3a to 3n, respectively Pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolinium, pyrrolium, thiazolium And triazolium.

(3)

(Wherein, R ₁₂ to R ₁₇ are each independently an alkyl group having 1 to 9 carbon atoms or a phenyl group).

As an anion constituting the ionic liquid is ^{F -, Cl -, Br -} , I -, NO 3 -, (CN) 2 N -, BF 4 -, ClO 4 -, RSO 3 - ( wherein, R is C 1 -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.

As an additive, 1 type chosen from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite, and fluoroethylene carbonate (FEC) can be used individually or in combination of 2 or more types.

By performing the aging treatment on the electrochromic device using the electrolyte containing the above-mentioned additive, the stability of the SEI film formed on the surface of the negative electrode can be enhanced and the internal resistance can be reduced compared with before aging treatment. By reducing the internal resistance in the process of manufacturing such an electrochromic device (that is, before shipment), it is possible to increase the durability of the device to high temperature preservation thereafter and to manufacture an electrochromic device having excellent durability. The amount of the additive contained in the nonaqueous electrolyte solution is preferably in the range of approximately 0.05 to 5 wt% (more preferably approximately 0.1 to 1 wt%).

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. 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. The conductive material may be deposited on the substrate by a known method such as sputtering, electron beam deposition, chemical vapor deposition, or sol-solid coating, to form a transparent conductive layer.

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 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  1-7 and Comparative Example  1-2

1.solid Polymer  Preparation of electrolyte composition

To prepare a solid polymer electrolyte composition with the components and composition ratios shown in Table 1.

division Spacer
(weight%) Acrylic compound
(B)
(weight%) Polymer (C)
(weight%) Photopolymerization initiator (D)
(weight%) Metal salt
(E)
(weight%) Ionic liquid
(F)
(weight%) ingredient weight Example 1 A-1 3 42 42 One 8 4 Example 2 A-1 3 44 44 One 8 - Example 3 A-2 3 44 44 One 8 - Example 4 A-3 3 44 44 One 8 - Example 5 A-1 One 45 45 One 8 - Example 6 A-4 3 44 44 One 8 - Example 7 A-1 9 41 41 One 8 - Comparative Example 1 - - 43.5 43.5 One 8 4 Comparative Example 2 - - 45.5 45.5 One 8 - A-1: Acrylic resin-based spacers (80 占 퐉)
A-2: Acrylic resin-based spacers (5.5 占 퐉),
A-3: Silicon-based spacers (2.5 占 퐉),
A-4: Acrylic resin-based spacers (160 탆),
B: DPHA (dipentaerythritol hexaacrylate)
C: methoxy PEG 600 methacrylate (MPEG600MA)
D: OXE-01 (1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ciba company)
E: 1 M LiClO ₄
F: 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, [BMI-TFSI]

2. Manufacture of electrochromic devices

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. Injecting the solid polymer electrolyte compositions of Examples 1 to 7 and Comparative Examples 1 and 2 into the prepared intermediate and sealing the inlet with a sealant, and then irradiated with an ultraviolet (UV) exposure machine for 1 minute to in-situ polymerization The discoloration element was produced.

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.solid Polymer  Ionic conductivity of electrolyte

The ionic conductivity is about 10 ^-2 S / cm in the liquid electrolyte, but in the case of the solid electrolyte, the ionic conductivity is determined by the degree of curing and the content of the acryl-based compound, and the ionic conductivity is measured using the measuring device (Inolab multi 740). It was measured by.

<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.

<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

The stability of the product was confirmed by measuring the electrochromic behavior of the electrochromic device (coloration 3V 20 sec / decoloration -3V 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. Electrochromism (staining / Decoloration ) Time Reflectivity (%)

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 ◎ ◎ ◎ 38/68 Example 2 ◎ ◎ ◎ 38/66 Example 3 ◎ ◎ ○ 37/67 Example 4 ◎ ◎ ○ 40/65 Example 5 ◎ ◎ ○ 39/66 Example 6 ◎ ○ ◎ 42/65 Example 7 △ △ ◎ 50/67 Comparative Example 1 ◎ ◎ × 51/65 Comparative Example 2 ◎ ◎ × 52/66

Referring to Table 2 above, the solid polymer electrolytes of Examples 1 to 7 exhibited ionic conductivity similar to that of the partially commercialized gel electrolyte, and the polymerization reaction according to the photocuring was promoted and the degree of curing was easily controlled, as well as shrinkage or expansion. Due to the small volume change, the product and process stability were excellent, and the reflectance characteristics according to the electrochromic color were also excellent.

However, in Example 6, in which a spacer having a size of 160 μm was added, the polymerization time increased as the amount of the cured electrolyte in the large area electrochromic device increased, and the response time of discoloration and discoloration also increased slightly.

On the other hand, in the case of Comparative Examples 1 and 2, the thickness of the electrolyte solution cured when the positive electrode and the negative electrode were combined or the gel electrolyte was hardened in the large-area cell because the spacer was not added and the cell gap could not be maintained was not maintained. It was confirmed that the stability and electrochromic performance of the decrease.

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 (11)

A solid polymer electrolyte composition comprising a spacer.
The method of claim 1, wherein the spacer is silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, acrylic acid, methacrylic acid, polyimide, aromatic polyamide, polybenzoimidazole, A solid polymer electrolyte composition formed of at least one member selected from the group consisting of siloxane resin, glass, silicone, and curable resin composition.
The solid polymer electrolyte composition of claim 1, wherein the spacer is included in an amount of 0.01 to 5 wt% based on the total weight of the composition.
The solid polymer electrolyte composition of claim 1, further comprising a polymer, a 4 to 6 functional acrylic compound, a polymerization initiator, a metal salt, and an ionic liquid.
The solid polymer electrolyte composition of claim 4, wherein the polymer is represented by Formula 1 below:
[Chemical Formula 1]

(Wherein R1 is an alkoxy group having 1-6 carbon atoms; R2 is a hydrogen atom, an alkyl group having 1-6 carbon atoms or

; R3 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; n is an integer from 2-70.
The solid polymer electrolyte composition of claim 4, wherein the 4 to 6 functional acrylic compound comprises a compound represented by the following Chemical Formula 2:
(2)

(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 &}

being).
The method of claim 4, wherein the ionic liquid is ammonium, imidazolium, oxazolium, piperidinium, pyrazinium, pyrazolium, pyridazinium, pyridinium, pyrimidinium, pyrrolidinium, pyrrolinium, pyrrolium , with a cation selected from the group consisting of thiazolium and ^{triazolium, 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 -, (}} 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 A solid polymer electrolyte composition consisting of a combination of anions.
The metal salt of claim 4, wherein the metal salt is a cation selected from the group consisting of Li ⁺ , Na ⁺ , K ^+, and 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 (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 ^- alkali metal salt composed of a combination of ion anion selected from the group consisting of a solid polymer electrolyte composition.
The solid polymer electrolyte composition according to claim 4, 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 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 10, wherein the electrolyte is in-situ polymerized between the first and second electrodes.

Images