KR102136547B1 - An electrolyte composition, an electrolyte film, and an electrochromic device - Google Patents

Abstract

The present application relates to a composition, a gel polymer electrolyte and an electrochromic device. The electrolyte composition of the present application, by including a polymer formed from a predetermined monomer, provides an excellent memory effect to the gel polymer electrolyte and the electrochromic device.

Description

An electrolyte composition, an electrolyte film, and an electrochromic device

The present application relates to an electrolyte composition, an electrolyte film, and an electrochromic device.

Electrochromic refers to a phenomenon in which the optical properties of an electrochromic material are changed by an electrochemical oxidation or reduction reaction, and a device using the phenomenon is called an electrochromic device. In general, an electrochromic device includes an electrolyte, an electrode, and an electrochromic layer.

The electrolyte used in the electrochromic layer can be divided into liquid and solid electrolytes. The liquid electrolyte has a high ionic conductivity, but there is a problem in that the electrolytic solution leaks or polarizes as the electrolyte moves downward due to gravity, thereby deteriorating the driving characteristics of the device. This problem is prominent when manufacturing large-area devices. Considering the problem of using the liquid electrolyte as described above, a polymer film, that is, a solid gel polymer electrolyte is used. However, the gel polymer electrolyte has a problem that the ion conductivity is lower than that of the liquid electrolyte. In addition, the gel polymer electrolyte requires durability, heat resistance, high permeability, and low haze so as not to decompose even under a driving voltage. In particular, when a gel polymer electrolyte is used in an electrochromic device for a smart window or an automobile sunroof, memory characteristics in which coloring and decoloring states are maintained for a considerable time should be considered even when no voltage is applied.

Republic of Korea Patent Publication No. 10-2011-0003505

One object of the present application is to provide a composition for a gel polymer electrolyte capable of imparting excellent memory characteristics to an electrochromic device.

Another object of the present application is to provide a gel polymer electrolyte having high transmittance and low haze and an electrochromic device comprising the same.

The above and other other objects of the present application can be solved by the present application described in detail below.

As an example of this application, this application relates to an electrolyte composition. The electrolyte composition of the present application may include (A) a polymer containing a predetermined compound as a polymerization unit, (B) a photocurable monomer, (C) a monovalent metal salt, and (D) an initiator.

The polymer (A) may include a polycarbonate diol-derived polymerization unit, a diisocyanate compound-derived polymerization unit, and a hydroxy group-containing alkyl (meth)acrylate-derived polymerization unit. In the present application, the term "polymerization unit" may mean a state in which the predetermined monomer is polymerized and contained in a main chain or a side chain of a polymer or a polymerization reaction product formed by polymerization of a predetermined monomer that is one impression. The polymer (A) can impart high temperature durability, heat resistance, and transparency to the gel polymer electrolyte, and improve the memory effect of the electrochromic device.

In one example, the polymerized unit derived from the polycarbonate diol included in the polymer (A) may be derived from a reactant between a carbonate compound and two different diol compounds.

The type of carbonate compound is not particularly limited. For example, dialkyl carbonate, diaryl carbonate, or alkylene carbonate can be used. More specifically, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, or ethylene carbonate may be used as a carbonate compound, but is not particularly limited to these compounds.

The two diol compounds reacting with the carbonate compound may each include alkylene groups having different carbon numbers. Specifically, the two diol compounds may be a compound of Formula 1 and a compound of Formula 2 below.

[Formula 1]

HO-R ₁ -OH

[Formula 2]

HO-R ₂ -OH

However, in Formula 1, R ₁ is an alkylene group having 2 to 5 carbon atoms, and in Formula 2, R ₂ is an alkylene group having 6 to 12 carbon atoms.

As the diol of Formula 1, for example, 1,4-butanediol may be used, and as the diol of Formula 2, 1,6-hexane diol may be used, but is not limited thereto.

In one example, the polymerization unit derived from the polycarbonate diol may be represented by the following formula (3).

[Formula 3]

However, in Chemical Formula 3, n and m may each independently be 10 to 50, R ₁ is an alkylene group having 2 to 5 carbon atoms, and R ₂ may be an alkylene group having 6 to 12 carbon atoms.

In one example, the polymer (A) may include polymerized units derived from a diisocyanate compound at both ends of Formula 3. Although not particularly limited, diisocyanate compounds include various known isocyanate compounds of aliphatic, cycloaliphatic or aromatic. More specifically, the carboxyl groups of tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer acid are converted to isocyanate groups. Aliphatic diisocyanates such as one dimer diisocyanate; 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Alicyclic diisocyanates such as isocyanate and 1,3-bis(isocyanatemethyl)cyclohexane; Or xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-di Phenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene di Aromatic diisocyanates such as isocyanate, 3,3'-dimethyl-4,4'-biphenylenediisocyanate, phenylenediisocyanate, and m-tetramethylxylylenediisocyanate can be used in this application.

In one example, the polymer (A) may include a double bond between carbons of a polymerization unit derived from a hydroxy group-containing alkyl (meth)acrylate at both ends. In this case, the polymer (A) has a structure in which a reactant of a diisocyanate compound and a hydroxy group-containing alkyl (meth) acrylate, that is, a polymerization unit derived from urethane acrylate, is bonded to both ends of the unit represented by the formula (3). Can. The carbon-to-carbon double bond can be used for light curing. As an example of a hydroxy group-containing alkyl (meth)acrylate, hydroxy ethyl acrylate, hydroxy ethyl methacrylate, or hydroxy butyl acrylate may be used, but is not limited thereto. For example, the polymer (A) is a urethane acrylic obtained from isophorone diisocyanate and hydroxyethyl methacrylate at both ends of the unit represented by Formula 3 obtained from a reactant between diethyl carbonate, butanediol, and hexanediol. The rate-derived polymerization unit may have a combined structure. The polymer (A) may have a structure as shown in Formula 4 below.

[Formula 4]

However, in Chemical Formula 4, n and m may be independently 10 to 50, respectively.

In one example, the polymer (A) may be an oligomer having a weight average molecular weight (M _w ) of 50,000 or less. If the molecular weight is higher than this, it may be difficult to achieve the desired purpose, and the fluidity is lowered, and the processability is poor. Specifically, the polymer (A) may have a molecular weight of 1,000 or more, 3,000 or more, 5,000 or more, or 10,000 or more, and may have a molecular weight of 50,000 or less or 45,000 or less. In the present application, the weight average molecular weight may mean a converted value for standard polystyrene measured by GPC (Gel Permeation Chromatograph).

In general, oligomers are used to reinforce mechanical properties and the like that cannot be obtained by using only curable monomers. It is not easy to apply oligomers satisfying various properties required for gel polymer electrolytes. However, the polymer (A) of the above-mentioned structure is not only excellent in transparency in itself, but also has high compatibility with an organic solvent, and thus does not phase-separate with an organic solvent, and thus can provide an electrolyte film having high light transmittance and low haze. . In addition, the electrolyte film containing the polymer (A), as described below, not only has the ionic conductivity required to drive the electrochromic device, but can also provide an excellent memory effect to the device.

The photocurable monomer (B) is a material capable of forming a matrix of a gel polymer electrolyte upon curing of the electrolyte composition. In the present application, as the photo-curable monomer, a monofunctional monomer having a hydroxy group or a carboxyl group; Or a polyfunctional acrylate monomer can be used.

The type of the photocurable monofunctional monomer is not particularly limited. For example, as the monofunctional monomer, a hydroxy group-containing monomer such as vinyl acetate or hydroxyalkyl (meth)acrylate may be used, or a carboxyl group-containing monomer such as (meth)acrylic acid, itaconic acid, or maleic acid may be used. Can.

The type of the photo-curable polyfunctional acrylate is also not particularly limited. For example, hexanediol diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), ethylene glycol diacrylate (EGDA), trimethylolpropane triacrylate (trimethylolpropane triacrylate, TMPTA) ), trimethylolpropane ethoxylated triacrylate (TMPEOTA), glycerol propoxylated triacrylate (GPTA), pentaerythritol tetraacrylate (PETA), or dipentaerythrate Ditolerythritol hexaacrylate (DPHA) and the like can be used as the photocurable polyfunctional monomer.

The (C) monovalent metal salt may mean a compound capable of providing Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ . These alkali metal salts may be involved in the reaction for electrochromic. Although not particularly limited, for example, when Li ⁺ is used in the electrochromic reaction, the monovalent metal salt (C) includes LiPF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiTFSI, LiBF ₄ , LiSbF ₆ , LiN(C ₂ F ₅ SO ₂ ) ₂ , LiAlO ₄ , LiAlCl ₄ , LiCo _{0 . 2} Ni _{0 . 56} Mn _{0 .} Lithium salts such as ₂₇ O ₂ , LiCoO ₂ , LiSO ₃ CF ₃ or LiClO ₄ can be used.

The type of the (D) initiator is not particularly limited. For example, commercial products such as Irgacure 184, Irgacure 500, Irgacure 651, Irgacure 369, Irgacure 907, Darocur 1173, Darocur MBF, Irgacure 819, Darocur TPO, Irgacure 907, Esacure KIP 100F can be used.

In one example, the composition may further include an organic solvent (E). The type of the organic solvent is not particularly limited, but may be, for example, a carbonate-based solvent. The carbonate-based solvent has a high dielectric constant and can increase the ion conductivity of ions derived from monovalent metal salts. As the carbonate-based solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethylmethyl carbonate (EMC) may be used.

Although not particularly limited, the composition may include 10 to 70 parts by weight of the (C) monovalent metal salt and the (E) organic solvent, and 30 to 90 parts by weight of the (A) polymer. In the present application, "part by weight" may mean a weight ratio between components to be compared.

In another example, the composition includes 0.1 to 5 parts by weight of the (B) photocurable monomer, compared to 100 parts by weight of the (A) polymer, (C) the monovalent metal salt, and (E) the organic solvent. can do. In addition, the composition may include 0.01 to 1 part by weight of the (D) initiator, compared to 100 parts by weight of the (A) polymer, (C) the monovalent metal salt, and (E) the organic solvent.

In one example, the electrolyte composition may have a viscosity before curing of 10,000 cps or less measured by the method described in Examples below. For example, the lower limit of the viscosity may be 100 cps or more, 500 cps or more, 1,000 cps or more, or 2,000 cps or more, and the upper limit of the viscosity may be 8,000 cps or less, 6,000 cps or less, or 4,000 cps or less. When having a viscosity in the above range, it may have excellent adhesion even after curing. Therefore, the use of a separate adhesive may be omitted even in the case of laminating with an adjacent layer structure during device fabrication. In addition, since it has excellent coating processability when it has a viscosity in the above range, it is also advantageous for a large-area mass production process using R2R.

In another example related to the present application, the present application relates to an electrolyte film. The electrolyte film of the present application may be a gel polymer electrolyte (GPE) comprising a cured product of the composition described above. The conditions for curing the composition are not particularly limited, and for example, curing may be performed by irradiating light having a wavelength of 200 nm to 500 nm for several seconds to several minutes.

In one example, the electrolyte film may have a thickness in the range of 10 to 300 μm. The electrolyte film having the above range may have excellent processability and heat resistance.

In another example, the light transmittance of the electrolyte film may be about 75% or more, 80% or more, or 85% or more. In addition, haze may be 2% or less. In the case of having a transmittance and/or haze in the above numerical range, high transparency can be achieved. Light in relation to transmittance may mean light having a wavelength of about 380 nm to 780 nm, specifically light having a wavelength of 550 nm, and the transmittance may be a UV-Vis spectrometer (LS162 Transmission meter of Linshang). Can be measured.

In another example, the electrolyte film may have a modulus of 0.5 MPa or more. Specifically, the modulus value of the electrolyte film may be 0.7 MPa or more, 0.9 MPa or more, 1.1 MPa or more, 1.3 MPa or more, 1.5 MPa or more, or 1.7 MPa or more. Although not particularly limited, the upper limit of the modulus value may be 5 MPa. At this time, the modulus may be measured at 25 ℃ room temperature and 0.1 mm / s tensile speed.

In another example of the present application, the present application relates to an electrochromic device. The electrochromic device includes an electrolyte film, an electrode layer, and an electrochromic layer. As the electrolyte film, a film having the same configuration as mentioned above can be used.

The type of the electrode layer is not particularly limited. For example, the electrode layer may include a transparent conductive compound, a metal mesh, or OMO (oxide/metal/oxide).

In one example, the transparent conductive compound used in the electrode layer, ITO (Indium Tin Oxide), In ₂ O ₃ (indium oxide), IGO (indium galium oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium doped) Zinc Oxide (Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), IZO (Indium doped Zinc Oxide), NTO (Niobium doped Titanium Oxide), ZnO (zink oxide), or CTO (Cesium Tungsten Oxide) For example. However, the material of the transparent conductive compound is not limited to the materials listed above.

In one example, the metal mesh used in the electrode layer includes Ag, Cu, Al, Mg, Au, Pt, W, Mo, Ti, Ni or alloys thereof, and may have a lattice shape. However, the materials usable for the metal mesh are not limited to the metal materials listed above.

In one example, the electrode layer may include OMO (oxide/metal/oxide). Since the OMO has a lower surface resistance than the transparent conductive oxide represented by ITO, it is possible to improve the electrical properties of the electrochromic device, such as shortening the discoloration rate of the electrochromic device.

The OMO may include an upper layer, a lower layer, and a metal layer positioned between the two layers. In the present application, the upper layer may mean a layer positioned relatively farther from the electrolyte layer among the layers constituting the OMO.

In one example, the upper and lower layers of the OMO electrode are Sb, Ba, Ga, Ge, Hf, In, La, Se, Si, Ta, Se, Ti, V, Y, Zn, Zr or oxides of these alloys ( oxide). The types of metal oxides included in the upper layer and the lower layer may be the same or different. In addition, the metal layer included in the OMO electrode may include a low-resistance metal material. Although not particularly limited, for example, one or more of Ag, Cu, Zn, Au, Pd, and alloys thereof may be included in the metal layer.

In one example, the electrochromic device may include a plurality of electrode layers. For example, the electrochromic device may sequentially include a first electrode layer, an electrochromic layer, an electrolyte film, and a second electrode layer.

The electrochromic layer may include an electrochromic material, that is, an electrochromic metal oxide.

In one example, the electrochromic layer may include a reducing inorganic discoloration material in which coloration occurs during a reduction reaction. The type of the reducing inorganic discolorant that can be used is not particularly limited, for example, oxides of Ti, Nb, Mo, Ta or W, such as WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O ₅ or TiO _2, etc. It can be used for this electrochromic layer.

In another example, the electrochromic layer may include an oxidative color change material that is colored when the material is oxidized. Oxides of Cr, Mn, Fe, Co, Ni, Rh, or Ir, such as, for example, LiNiOx, IrO ₂ , NiO, V ₂ O ₅ , LixCoO _{2 ,} Rh ₂ O ₃ or CrO ₃ ; And it may include one or more selected from prussian blue (prussian blue).

In one example, the electrochromic device of the present application may further include an ion storage layer. The ion storage layer may mean a layer formed in order to balance charge with the electrochromic layer during a reversible oxidation/reduction reaction for discoloration of an electrochromic material. The ion storage layer may be located between the second electrode layer and the electrolyte layer.

The ion storage layer may include an electrochromic material having different color development characteristics from the electrochromic material used in the electrochromic layer. For example, when the electrochromic layer includes a reducing electrochromic material, the ion storage layer may include an oxidative electrochromic material. Also, the reverse is also possible.

In one example, the electrochromic device may further include a transparent substrate. The light transmittance of the substrate may be, for example, 75% or more. The material of the translucent base is not particularly limited, and a known resin or glass can be used. The substrate may be located on the outer surface of the device as shown in FIG. 1.

This application can provide an excellent memory effect for an electrochromic device used in a smart window, automobile sunroof, or glass. As a result, it is possible to reduce the voltage consumption and improve the long-term driving durability of the device.

1 schematically shows a cross-section of an electrochromic device according to an example of the present application.
FIG. 2 shows a memory effect of an example device and a comparative example device through a change in light transmittance after power off.
FIG. 3 is an image taken 24 hours after power-off of the Example and Comparative Example elements in which the power was turned off in a discolored state.
4 is a result of NMR analysis of GPE used in each of Examples and Comparative Examples.
5 is a modulus measurement result for the GPE used in each of the Examples and Comparative Examples.

Hereinafter, the present application will be described in detail through examples. However, the protection scope of the present application is not limited by the examples described below.

<Measurement method>

* Molecular weight of polymer (A): The weight average molecular weight (Mw) was measured under the following conditions using GPC, and standard polystyrene of the Agilent system was used for the preparation of the calibration curve.

<condition>

Meter: Agilent GPC (Agilent 1200 series, U.S.)

Column: 2 PL Mixed B connections

Column temperature: 40℃

Eluent: THF (Tetrahydrofuran)

Flow rate: 1.0 mL/min

Concentration: ~ 1 mg/mL (100μL injection)

* Viscosity of the composition: Using a Brookfield Viscometer (LV type, #63 spindle), the viscosity before curing of the composition prepared according to Examples and Comparative Examples was measured.

* Ion conductivity: Ionic conductivity was measured using EIS (Electrochemical impedance spectroscopy). Specifically, a coin cell containing GPE in the form of a film was sandwiched between circular SUS plates, the jigs were connected, and ion conductivity was measured using a Nyquist plot.

* GPE Light transmittance ( % ) and haze ( % ): After curing the composition prepared according to Examples and Comparative Examples, light transmittance and haze for a wavelength of 550 nm using a UV-Vis spectrometer (LS162 Transmission meter from Linshang) Was measured.

* Measurement of memory effect: The device was colored and bleached while applying ± 2V voltage (driving voltage) alternately for 100 seconds each. After 100 cycles, the power of the first colored device was turned off, and the transmittance immediately after off and the change in transmittance after 48 hours were observed. Similarly, after 100 cycles, the first colored element was decolored, and after the power of the decolored element was turned off, the transmittance immediately after off and the change in transmittance after 48 hours were observed.

* Hard segment : Measured using TD NMR equipment. The results are shown in FIG. 4. Specifically, Figure 4 shows the results of the FID experiment using NMR, the x-axis means the time the signal receiver is open in the NMR. In addition, the y-axis is a signal change during that time, and is a value measured by normalizing the signal to 100.

* Modulus ( Mpa ): After curing the composition prepared according to Examples and Comparative Examples, the modulus of GPE was measured using a universal testing machine from Zwick roell.

Example One

Preparation of polymer (A): Polymer corresponding to formula (4 ) (A) using diethyl carbonate, 1,4-butanediol, 1,6-hexanediol, isophorone diisocyanate, and hydroxyethyl methacrylate as monomers ). The weight average molecular weight (M _w ) of the prepared polymer was 15,000.

Preparation of composition and GPE : Content (g) ratio of 10:10:0.3:0.033 of polymer (A), organic solvent (PC) containing 2M of LiClO ₄ , acrylic acid, and photoinitiator (Ciba Corporation, Irgacure 819) It was mixed to prepare a composition. The composition was applied on a PET substrate and irradiated with light having a wavelength of about 400 nm for about 1 minute to obtain an electrolyte film having a thickness of 150 μm. The size of the cut electrolyte film is 5 cm X 5 cm. Composition and properties of the composition and GPE are shown in Table 1 below.

Preparation of electrochromic device: ITO electrode (150 ohm/m ² ), 350 nm thick WO ₃ thin film, GPE of Example 1, 450 nm thick Prussian Blue (PB) thin film, and ITO electrode (150 ohm/m ² ) An electrochromic device laminated in this order was manufactured. The measurement results of the memory characteristics of the fabricated device are shown in Table 2 and FIG. 2.

Example 2

A composition, a GPE, and a device were prepared in the same manner as in Example 1, except that the composition and viscosity included in the composition were changed as shown in Table 1 below.

Comparative example One

A composition, a GPE, and a device were prepared in the same manner as in Example 1, except that the polymer (B) was used instead of the polymer (A) and the viscosity of the electrolyte composition for GPE was changed as shown in Table 1 below.

Preparation of polymer (B): PPG based urethane diacrylate (weight average molecular weight 15,000) was prepared by synthesizing propylene glycol and isocyanate.

Comparative example 2

The composition, GPE, and device were prepared in the same manner as in Example 1, except that the polymer (C) was used instead of the polymer (A), and the viscosity of the electrolyte composition for GPE was changed as shown in Table 1 below.

Preparation of polymer (C): A urethane-based polymer (c1) obtained by reacting INDI (isononane diisocyanate, isomer) and DEPD (2,4-diethylpentane-1,5-diol) was prepared. In addition, an ester-based polymer (c2) obtained by reacting AdA (Adipic acid) with DEPD was prepared. Thereafter, the polymer obtained by reacting the polymer (c1) and the polymer (c2) together was polymerized with INDI and HBA (hydroxybutyl acrylate). The weight average molecular weight of the polymer (C) was 15,000.

[Table 1]

[Table 2]

It can be seen from Table 2 and FIGS. 2 to 3 that the memory effect of the electrochromic device manufactured according to the present embodiment is superior to that of the comparative example. This is considered to be because, in the case of Examples, the movement of lithium ions after voltage off is suppressed compared to Comparative Examples. It is believed that in addition to the properties of the material itself of the polymer (A), it is also related to the large modulus of the GPE formed from the polymer (A). That is, after voltage off, lithium ions move while hopping along a crosslinked chain in the GPE. Since the GPE of the present application having a large modulus has a rigid property, mobility of lithium ions as well as GPE is mobility. ) Is suppressed, it is thought that the memory effect is improved.

On the other hand, the result of FIG. 4 includes information related to T2 relaxation. The more rigid a molecule is, that is, the more hard segments, the faster the T2 relaxation and the faster the signal decrease. In Fig. 4, it is confirmed that the signal reduction of the example is faster than that of the comparative example, which is consistent with the above analysis on the rigid properties. In addition, as the number of hard segments increases due to the rigidity of the molecules, the value of the modulus increases. Referring to FIG. 5, it is confirmed that the modulus value of the embodiment in the tensile strength test is larger.

Claims (18)

(A) a polymer comprising a polycarbonate diol-derived polymerization unit, a diisocyanate compound-derived polymerization unit, and a hydroxyl group-containing alkyl (meth)acrylate-derived polymerization unit;
(B) photo-curable monomers;
(C) monovalent metal salts; And
(D) initiator;
It includes,
The polycarbonate diol-derived polymerization unit is an electrolyte composition represented by the following formula (3):
[Formula 3]

However, in Formula 3, n and m are each independently 10 to 50, R ₁ is an alkylene group having 2 to 5 carbon atoms, and R ₂ is an alkylene group having 6 to 12 carbon atoms. The electrolyte composition according to claim 1, wherein the polycarbonate diol-derived polymerization unit comprises a carbonate compound-derived polymerization unit, a compound-derived polymerization unit, and a compound-derived polymerization unit:
[Formula 1]
HO-R ₁ -OH
[Formula 2]
HO-R ₂ -OH
However, in Formula 1, R ₁ is an alkylene group having 2 to 5 carbon atoms, and in Formula 2, R ₂ is an alkylene group having 6 to 12 carbon atoms. delete The polymer composition according to claim 1, wherein the polymer (A) includes polymerized units derived from a diisocyanate compound at both ends of the formula (3). The electrolyte composition according to claim 4, wherein the polymer (A) contains double bonds between carbons of a polymerization unit derived from a hydroxy group-containing alkyl (meth)acrylate. The electrolyte composition according to claim 1, wherein the polymer (A) has a weight average molecular weight (Mw) of 50,000 or less. According to claim 1, wherein the photocurable monomer (B) is a monofunctional monomer having a hydroxyl group or a carboxyl group; Or a polyfunctional acrylate monomer electrolyte composition. The electrolyte composition according to claim 1, wherein the (C) monovalent metal salt is a lithium salt. The electrolyte composition according to claim 1, further comprising (E) an organic solvent. The electrolyte composition of claim 1 having a viscosity in the range of 100 cps to 10,000 cps. An electrolyte film comprising a cured product of the electrolyte composition according to any one of claims 1, 2, 4 to 10. The electrolyte film according to claim 11, wherein the modulus is 0.5 MPa or more. Electrode layer; The electrolyte film according to claim 11; And an electrochromic layer. 14. The electrochromic device according to claim 13, which sequentially comprises a first electrode layer, an electrochromic layer, an electrolyte film, and a second electrode layer. 15. The electrochromic device of claim 14, wherein the electrochromic layer comprises a reducing electrochromic material or an oxidative electrochromic material. 16. The electrochromic device according to claim 15, wherein the reductive electrochromic material is an oxide of Ti, Nb, Mo, Ta or W. 16. The method of claim 15, wherein the oxidative electrochromic material is Cr, Mn, Fe, Co, Ni, Rh, or an oxide of Ir; And Prussian Blue. 16. The electrochromic device of claim 15, further comprising an ion storage layer between the electrolyte film and the second electrode layer, the ion storage layer comprising an electrochromic material having different color development characteristics from the electrochromic layer.

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