WO2019054720A1 - Method for manufacturing electrochromic device - Google Patents

Abstract

The present application relates to a method for manufacturing an electrochromic device. The manufacturing method of the present application manufactures a device by inserting, in advance, a monovalent cation into a reductive electrochromic layer through a dry process, and then laminating the colored electrochromic layer, an electrolyte layer and an ion storage layer containing an oxidative chromic material, which is itself in a colored state. Therefore, the present application can improve the operation durability of an electrochromic device.

Description

Method for manufacturing electrochromic device

Mutual citation with related applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0119271 and Korean Patent Application No. 10-2018-0106524 filed on September 18, 2017, The contents of which are incorporated herein by reference.

Technical field

The present application relates to a method of manufacturing an electrochromic device.

The term " electrochromism " refers to a phenomenon in which an optical property of an electrochromic material is changed by an electrochemical oxidation or reduction reaction. The electrochromic device is a device using the phenomenon described above. The electrochromic device generally includes an electrochromic layer, an electrolyte layer, and an ion storage layer between two opposing electrodes, and each of the electrochromic layer and the ion storage layer contains a discoloring substance whose reaction for color development is opposite to each other do. For example, the electrochromic layer may contain WO ₃ , which is transparent in itself but is colored blue when subjected to a reduction reaction, and the ion storage layer may contain an oxidized state (Fe ^III [Fe ^II (CN) ₆ ] ^- ) Prussian blue (PB), which has a blue color and changes in transparency during the reduction reaction, may be included.

In this way, when the discoloring materials having opposite colors to each other are used in different layers, it is necessary to match the states of the respective layers before driving the actual device in order to drive the electrochromic device. Specifically, it is necessary to take measures such that both the electrochromic layer and the ion storage layer are in a colorless or transparent state (a discolored state) or both of them have a predetermined color (colored state). Conventionally, after the electrochromic device in which all of the constituent layers such as the electrode layer, the electrochromic layer, the electrolyte layer and the ion storage layer are laminated, and before the actual driving, an electrochromic material having an oxidative electrochromic material such as PB A voltage higher than the driving potential was applied to the layer for a predetermined time to forcibly insert the electrolyte ions, and the PB was subjected to a decoloring (reduction) treatment. Such an operation is called a so-called initialization operation. However, a discoloring substance such as PB, which is subjected to decolorization (reduction) treatment, does not have ions (electrolytes) participating in the discoloration reaction per se. In addition, when a gel polymer electrolyte is used in the device, a liquid electrolyte is used There is a problem that the amount of the electrolytic ion is smaller than that of the case. Therefore, overvoltage is required to completely decolorize the PB. However, the overvoltage causes deterioration of the electrode layer and the electrochromic layer, resulting in deterioration of driving durability of the device.

One object of the present invention is to provide an electrochromic device improved in driving durability and a method of manufacturing the same.

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

In one example of this application, the present application relates to a method of manufacturing an electrochromic device. Specifically, the present invention relates to a method of manufacturing an electrochromic device in which an electrolyte layer and an ion storage layer are successively placed on an electrochromic layer containing a reducing electrochromic material.

In the present application, except for the structure of the electrochromic layer and the ion storage layer in which the transmittance is significantly lowered during coloring, each layer structure used in the electrochromic device of the present application has a transmittance of 80% or more with respect to a visible light wavelength in the range of 380 to 780 nm Or 85% or more.

The manufacturing method of the present application includes the step of inserting monovalent cations into the electrochromic layer before placing the electrolyte layer on the electrochromic layer. Through the insertion of the monovalent cation, the electrochromic layer in the electrochromic layer can be reduced and the electrochromic layer can be colored. Accordingly, the electrochromic layer in which the monovalent cation is inserted may have a colored state in the same manner as the ion storage layer containing the oxidative electrochromic material, and as a result, The device may not require initialization.

In the present application, the insertion of monovalent cations to the electrochromic layer can be accomplished by a dry process. For example, the insertion of monovalent cations to the electrochromic layer can be performed by deposition. As described below, when monovalent cations are inserted by a dry process, there is an advantage that the electrochromic layer has an excellent adhesion to the adjacent layer and a separate cleaning step is not required.

In one example, the monovalent cation insertion to the electrochromic layer can be accomplished by thermal evaporation or thermal evaporation deposition. According to the above method, a high heat in a vacuum state can be applied to the metal source to vaporize the metal into an ionic state and insert it into the electrochromic layer.

In one example, the monovalent cation that is inserted by deposition may be Li ⁺ , Na ⁺ , K ⁺ , Rb ^+, or Cs ⁺ . That is, in the thermal evaporation deposition, a metal such as Li, Na, K, Rb or Cs may be used as a source for the monovalent cation.

In the present application, the thermal evaporation, that is, the step of inserting monovalent cations, can be performed so that a separate layer (metal layer) composed of a source of monovalent cations is not formed. For example, in the case where lithium ion (Li ⁺ ) is to be inserted into the electrochromic layer, the thermal evaporation process of the present application may be such that no separate lithium layer is formed on the electrochromic layer. When a metal layer such as a lithium layer is formed, cell performance may be deteriorated. Further, the formation of the metal layer can increase the reflectivity inside the electrochromic device, which may hinder the function of the electrochromic device which provides low transparency in coloring and high transparency in decolorization.

The conditions of the thermal evaporation deposition are not particularly limited as long as the thermal evaporation is carried out to such an extent that a separate layer composed of a small amount of positive ions is not formed. For example, the thermal evaporation may be performed at a pressure of 10 mTorr or less, 5 mTorr or less, 3 mTorr or less, 1 mTorr or less, 0.1 mTorr or less, or 0.01 mTorr or less. The lower limit thereof is not particularly limited, but may be, for example, 0.0001 mTorr or more.

In one example, the thermal evaporation may be performed under a temperature condition where the melting point of the metal ion to be inserted is considered. For example, thermal evaporation can be performed at a temperature above the melting point of the source metal of monovalent cations. Specifically, when the monovalent cation to be inserted is Li ⁺ , the thermal evaporation may be performed at a temperature of 180 ° C or higher, which is the melting point of lithium, considering that the melting point of lithium is about 180 ° C. Specifically, the thermal evaporation may be performed at a temperature of about 500 to 700 占 폚.

The time for which the abnormal thermal evaporation deposition satisfying the above conditions is performed is not limited. For example, thermal evaporation may be performed for a few seconds to several minutes under the above-described pressure and temperature conditions.

In one example, when thermal evaporation is performed to such an extent that a monolayer does not form a separate layer composed of a source of a cation, the content of monovalent cations inserted into the electrochromic layer is 1.0 per cm ^{2 of the} electrochromic layer × 10 ^{- 8} mol to 1.0 × 10 ^{- 6} mol of the range, and more specifically may be within 5.0 × 10 ^-8 mol to 5.0 × 10 ^-7 mol range.

The content of the monovalent cations inserted into the electrochromic layer, that is, the number of moles can be obtained from the relationship between the amount of charge of the electrochromic layer in which monovalent cations exist and the mole number of electrons. For example, when a monovalent cation is inserted into the electrochromic layer using thermal evaporation deposition and the charge amount of the electrochromic layer is A (C / cm ² ), a value obtained by dividing the charge amount A by the Faraday constant F (A / F ) May be the number of moles of electrons present per cm < ² > of the electrochromic layer. On the other hand, since the electrons (e ^- ) and monovalent cations can react at a ratio of 1: 1, the maximum amount of monovalent cations present in the electrochromic layer, that is, the maximum number of moles may be equal to the number of electrons obtained from the above. The method of measuring the amount of charge in relation to the content of monovalent cations is not particularly limited. For example, the charge quantity can be measured by a known method such as potential step chronoamperometry (PSCA) using a potentiostat device.

In the present application, the form in which the inserted monovalent cation exists in the electrochromic layer may include all of the following cases. Specifically, the monovalent cation incorporated in the electrochromic layer in the present application may be contained in the electrochromic layer in the form of an ion and / or chemically bonded to the discoloring substance constituting the electrochromic layer. have.

In the present application, the electrochromic layer includes a reducing electrochromic material. In the present application, the reductive electrochromic material may be a material that undergoes coloration when subjected to a reduction reaction. When the monovalent cation is inserted into the electrochromic layer containing a reducing electrochromic material as described above, the electrochromic layer may have a discolored state, that is, a colored state.

The kind of the reducing electrochromic material usable in the electrochromic layer is not particularly limited. In one example, the electrochromic layer may comprise a reducing metal oxide that may be formed by a deposition method. For example, the electrochromic layer may be a deposition layer composed of at least one oxide selected from the group consisting of Ti, Nb, Mo, Ta, and W.

In the present application, the electrochromic layer may be formed by a dry coating method, for example, a vapor deposition method. The inventors of the present application have confirmed that the durability of the electrochromic device can be changed depending on the method of forming the electrochromic layer and the method of inserting the monovalent cation into the electrochromic layer. For example, when an electrochromic layer is formed by a wet coating method such as a heat treatment after applying a coating composition, rather than being formed by a dry coating method such as vapor deposition, a monovalent cation, which is not possessed by the electrochromic layer, As a method of introducing (or inserting) into the discoloration layer, a method of additionally adding a precursor capable of providing a monovalent cation to a coating composition containing a solvent and discolored particles such as WO ₃ can be considered . However, since the injection of the monovalent cation by the wet coating method proceeds in the organic electrolytic solution, if the cleaning step is not performed after the injection step, the adhering force to the laminated structure such as the electrolyte layer is lowered. As a result, Resulting in a problem of lowering drive durability. In particular, when a wet coating is applied, it is common to directly form an electrochromic layer by applying a composition containing an electrochromic material directly on the electrode. With respect to the electrode stack (electrode / electrochromic layer) having the electrochromic layer as described above, , There is a problem that cleaning is difficult for practical reasons such as loss of inserted electrolyte ions or damage to the stacked body. In addition, since the wet coating method described above is also unsuitable for a continuous manufacturing process of an electrochromic device using a roll-to-roll method, mass productivity is also poor. Taking this into consideration, in the present application, monovalent cations are injected into the electrochromic layer formed by the dry method by the dry method as described above.

In one example, the electrochromic layer may be formed by sputtering deposition. The process conditions of the sputtering deposition are not particularly limited. For example, sputter deposition may be performed at a pressure in the range of 1 mTorr to 100 mTorr, more specifically, at least 3 mTorr, at least 5 mTorr, or at least 10 mTorr and at most 80 mTorr, at least 60 mTorr, at least 40 mTorr, Under the following pressure conditions. More specifically, the sputtering deposition may be performed in a range of 50 W to 500 W, more specifically, 80 W or more, 100 W or more, 120 W or 130 W or more and 450 W or less, 400 W or less, 350 W or 300 W Or less. At this time, the flow rate of argon and oxygen gas to be used is not particularly limited. Further, the sputtering deposition under the above conditions can be performed within a range of several minutes to several hours.

In one example, the electrochromic layer may be formed on a conductive substrate or a release substrate. In each case, the insertion of the monovalent cation may be performed on the opposite surface of one side of the electrochromic layer in contact with the conductive substrate, or on the opposite surface of the electrochromic layer in contact with the releasable substrate. In the case where the electrochromic layer is formed on the release substrate, a step of laminating the electrochromic layer, which is a deposition layer, with a separately formed electroconductive substrate is required. Therefore, it is more preferable in terms of processability to directly form the electrochromic layer on the electroconductive substrate .

In one example, the electrochromic layer may be formed by a roll-to-roll method. For example, the method may be a method including a step of withdrawing the conductive film from a roll on which the conductive film is wound, and depositing an electrochromic layer on the electroconductive film. When the roll-to-roll method is used, it is advantageous in securing productivity and fairness.

In one example, the insertion of the monovalent cations can be effected on a laminate moving along a predetermined path in a roll-to-roll fashion. For example, when the laminate is a laminate including an electrically conductive substrate and an electrochromic layer sequentially, monovalent cations can be inserted into one surface of the electrochromic layer in the laminate.

In the present application, the thickness of the electrochromic layer is not particularly limited. For example, the thickness of the electrochromic layer may be 1 占 퐉 or less. Specifically, it may be 50 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more, and 900 nm or less, 700 nm or less, 500 nm or less, or 400 nm or less.

In one example, the electrochromic layer may be a layer formed on a conductive substrate. The conductive substrate in the present application may mean a layer capable of acting as a so-called electrode. In the present application, the conductive substrate may have a thickness in the range of, for example, 50 nm to 400 nm.

The kind of the material used for the conductive substrate is not particularly limited. For example, the conductive substrate may comprise a transparent conductive compound, a metal mesh, or an oxide / metal / oxide (OMO).

In one example, a transparent conductive oxide, ITO (Indium Tin Oxide), In 2 O 3 (indium oxide), IGO (indium galium oxide), FTO (Fluor doped Tin Oxide), (Aluminium doped Zinc Oxide) AZO, (GZO), antimony doped tin oxide (ATO), indium doped zinc oxide (IZO), niobium doped titanium oxide (NTO), zinc oxide (ZnO), or cesium tungsten oxide have. However, the materials listed above do not limit the material of the transparent conductive oxide.

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

In one example, the OMO may include an upper layer, a lower layer, and a metal layer provided between the two layers. The upper layer in the present application may mean a layer located relatively far from the electrolyte layer among the layers constituting the OMO. Since OMO has a lower sheet resistance than that of the transparent conductive oxide represented by ITO, the coloring speed of the electrochromic device can be shortened.

The upper and lower layers of the OMO electrode may include metal oxides of Sb, Ba, Ga, Ge, Hf, In, La, Se, Si, Ta, Se, Ti, V, Y, Zn, . The types of the metal oxides included in the upper layer and the lower layer may be the same or different. The thickness of the upper layer may range from 10 nm to 120 nm or from 20 nm to 100 nm. The refractive index of the upper layer may be in the range of 1.0 to 3.0 or in the range of 1.2 to 2.8. Having the refractive indices and thicknesses in the above range, an appropriate level of optical properties can be imparted to the device. Further, the thickness of the lower layer may be in the range of 10 nm to 100 nm or in the range of 20 nm to 80 nm. In addition, the visible light refractive index of the lower layer may range from 1.3 to 2.7 or from 1.5 to 2.5. Having the refractive indices and thicknesses in the above range, an appropriate level of optical properties can be imparted to the device.

The metal layer included in the OMO may comprise a low resistance metal material. Although not particularly limited, for example, at least one of Ag, Cu, Zn, Au, Pd, and alloys thereof may be included in the metal layer. In one example, the metal layer may have a thickness in the range of 3 nm to 30 nm, or in the range of 5 nm to 20 nm. In addition, the metal layer may have a visible light refractive index of 1 or less or 0.5 or less. When the refractive indices and the thicknesses are within the above ranges, an appropriate level of optical characteristics can be imparted to the conductive elements.

The electrolyte layer is a structure for providing electrolyte ions involved in the electrochromic reaction. Electrolyte ions may be inserted into the electrochromic layer and may participate in the discoloration reaction, and may be of the same kind as monovalent cations inserted into the electrochromic layer.

In one example, the electrolyte layer may be a gel polymer electrolyte (GPE). The gel polymer electrolyte can solve the problem of durability deterioration due to electrolyte leakage when using a liquid electrolyte. It is generally known that the ionic conductivity of a gel polymer electrolyte to an electrode is lower than that of a liquid electrolyte. However, in the present application, monovalent cations can be sufficiently transferred to the electrochromic layer by the thermal evaporation deposition as described above, so that it is possible to provide the electrochromic device with improved ionic transfer as compared with the prior art. This advantage can be confirmed by comparing the durability of the electrochromic device driven for a long time as in the following experimental example.

In one example, the gel polymer electrolyte layer may be formed from a crosslinkable monomer-containing composition capable of forming a polymer matrix upon crosslinking. Specifically, the gel polymer electrolyte is obtained by applying a composition comprising a crosslinkable monomer, a metal salt capable of providing a monovalent cation incorporated in the electrochromic layer, and an organic solvent onto a release substrate and then thermally or photo-curing Can be. The curing conditions are not particularly limited. The thickness of the electrolyte layer formed after curing may be, for example, about 50 nm or more, about 100 nm or more, about 500 nm or more, about 1 占 퐉 or more, and the upper limit may be about 200 占 퐉 or less, about 100 占 퐉 or less, Or about 10 탆 or less.

If the matrix formed after crosslinking can be transparent, the kind of the crosslinkable monomer is not particularly limited. For example, when the composition is photocured to form an electrolyte layer, a polyfunctional (meth) acrylate or the like may be used as the crosslinkable monomer.

The metal salt may be an alkali metal salt compound capable of providing a monovalent cation, for example, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ . The kind of the metal salt is not particularly limited. Examples of the alkali metal salt compound include LiPF ₆ , LiAsF ₆ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiBF ₄ , LiSbF ₆ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiAlO ₄ , LiAlCl ₄ , LiCo _{0 . 2} Ni _{0 . 56} Mn _{0 . 27} O ₂ , LiCoO ₂ , LiSO ₃ CF ₃ or LiClO ₄ , or a sodium salt compound such as NaClO ₄ may be used.

In one example, as the organic solvent, a carbonate compound may be used. Since the carbonate compound has a high dielectric constant, the conductivity of the electrolyte ion can be increased. As the carbonate compound, for example, propylene carbonate (EC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethylmethyl carbonate (EMC) may be used.

In one example, the composition used to form the electrolyte layer may further comprise a light or thermal initiator. These initiators can be of any known type without limitation.

The ion storage layer may mean a layer formed to match a charge balance with the electrochromic layer during a reversible oxidation / reduction reaction for discoloration of the electrochromic material. Accordingly, unlike the electrochromic layer, the ion storage layer includes an oxidative electrochromic material. In the present application, the oxidative electrochromic material may be a material which undergoes coloration when subjected to an oxidation reaction. For example, when electrolyte ions of the same kind as the univalent cations described above are inserted into an ion storage layer containing an oxidative electrochromic material, the ion storage layer may be discolored and have a state close to transparent.

The kind of the oxidative electrochromic material usable for the ion storage layer is not particularly limited. For example, the oxidative electrochromic material included in the ion storage layer may include at least one oxide selected from the group consisting of Cr, Mn, Fe, Co, Ni, Rh, and Ir; Or prussian blue, for example.

In one example, the ion storage layer may be formed by a wet coating method. Specifically, the ion storage layer may comprise at least one oxide particle selected from the group consisting of Cr, Mn, Fe, Co, Ni, Rh, and Ir; Or prussian blue particles on a substrate, followed by drying or heat treatment. Here, the substrate to which the coating composition is applied may be a release type substrate or a conductive substrate.

In one example, the particle diameter of the oxidative discoloration particles is not particularly limited, but may be, for example, 5 nm or more, 10 nm or more, or 15 nm or more, and 100 nm or less, 50 nm or less or 30 nm or less.

In one example, the coating composition for forming the ion storage layer may further comprise an organic solvent and / or a silane-based compound. The kind of the organic solvent or silane compound is not particularly limited and any known compound can be used without any limitation. For example, water or alcohol may be used as the organic solvent. As the silane compound, for example, a (meth) acrylic silane coupling agent, an epoxy silane coupling agent, an amino silane coupling agent, or an alkoxy silane coupling agent may be used as the silane compound. However, It is not.

The heat treatment conditions for the ion storage layer-forming composition are not particularly limited. For example, the heat treatment may be performed at a temperature of about 200 占 폚 or less by adding several seconds to several minutes or several seconds to several tens minutes. At this temperature, the alcohol solvent is removed, and at the same time, the solid storage layer can be formed as a result of condensation and hydrolysis of the silane-based compound. The lower limit of the heat treatment temperature is not particularly limited, but may be, for example, 70 ° C or higher, 75 ° C or higher, 80 ° C or higher, 85 ° C or higher, 90 ° C or higher, 95 ° C or higher or 100 ° C or higher.

In one example, when the ion storage layer is formed by a wet coating method, the ion storage layer may be a porous layer. In the case of the porous layer, it is possible to improve the long-term driving durability of the electrochromic device in that the migration of ions can be smoothly performed.

The thickness of the ion storage layer is not particularly limited. For example, the ion storage layer may have a thickness of 1 [mu] m or less. Specifically, it may be 50 nm or more, 100 nm or more, 150 nm or more, or 200 nm or more, and 900 nm or less, 700 nm or less, 500 nm or less, or 400 nm or less.

In one example, the ion storage layer may be a layer formed directly on the conductive substrate. That is, in the present application, the composition for forming the ion storage layer may be formed by applying directly on the conductive base material and then heat-treating the conductive base material. The conductive base material that is in direct contact with the ion storage layer may be referred to as a second conductive base material for the purpose of distinguishing the electrochromic layer from the adjacent conductive base material, and the specific structure thereof may be the same as that described above. In this case, the method of the present application may be a method including a step of laminating the layer structure so that the electrolyte layer, the ion storage layer, and the second conductive base material are sequentially positioned on one surface of the electrochromic layer. More specifically, the method further comprises laminating a first laminate comprising a conductive substrate and an electrochromic layer through a second laminate comprising a second conductive substrate and an ion storage layer and a gel polymer electrolyte layer . ≪ / RTI > At this time, a specific method for laminating the layer constitution is not particularly limited, and a known lamination method and the like can be suitably applied.

In one example, the ion storage layer may be a layer formed on the electrolyte layer. More specifically, a coating composition for forming an ion storage layer is applied on an electrolyte layer of a laminate including a laminate, an electrochromic layer and an electrolyte layer sequentially containing a conductive substrate, an electrochromic layer and an electrolyte layer in sequence And then dried to form a layer. Alternatively, it may be a layer formed by applying a coating composition for forming an ion storage layer on a gel polymer electrolyte layer existing on a release type substrate or as a single layer, followed by heat treatment.

In one example, the electrochromic device may further include a light-transmitting substrate on the outer surface of each conductive substrate. The type of the light-transmitting substrate is not particularly limited, and glass or a polymer resin can be used. For example, a polyester film such as PC (Polycarbonate), PEN (poly (ethylene naphthalate)) or PET (poly ethylene terephthalate), an acrylic film such as PMMA (poly (methyl methacrylate) Or a polyolefin film such as polypropylene (PP) or the like can be used as a light-transmitting substrate. As described above, when the electrochromic device further comprises a light-transmitting substrate, the method is characterized in that, prior to forming the electrochromic layer on the electroconductive substrate or before forming the ion storage layer on the second electroconductive substrate, And then forming the conductive base material having the above-described constitution on the base material.

According to one embodiment of the present application, in the present application, monovalent cations are already inserted into the electrochromic layer by a dry process before the interlayer arrangements for element formation, so that both the electrochromic layer and the ion storage layer are colored . Accordingly, since no separate initializing operation is required after laminating, it is possible to prevent the durability of the electrochromic device from deteriorating. Further, according to the present application, since the formation of the electrochromic layer and the insertion of monovalent cations can be formed in a roll-to-roll manner, the present application can improve the processability and productivity of the electrochromic device.

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

Method for measuring driving characteristics of electrochromic film

<Charge amount>

Examples and Comparative Examples Using the potential step chronoamperometry (PSCA) using a potentiostat device while increasing the driving cycle of the color-changing film, the charge amount of each film was measured, And the amount of charge after the elapse of 500 cycles are shown in Table 1.

<Transmittance>

* Transmittance at Coloring: It refers to the final coloring state transmittance observed after elapse of the time (50s) during which the potential for coloring is applied. Table 1 shows the colored film transmittance at the time of 500 cycle operation.

* Transmittance in decolorization: It refers to the final decolorized state transmittance observed after elapse of the time (50s) during which the potential for decolorization is applied. Table 1 shows the decolorized film transmittance at 500 cycles of operation.

<Discoloration rate>

* Coloring time (unit: second): The time taken to reach the level 80 when the transmittance of the final coloring state observed after elapse of the time (50s) for applying the potential for coloring is 100. Table 1 shows the time it takes for the decolorized film to be colored until it meets the above level at the time of 500 cycle operation.

* Decolorization time (unit: second): The time taken to reach the level of 80 when the final decolored state transmittance observed after elapse of the time (50s) for application of dislocation for decolorization is 100. Table 1 shows the time taken for the pigmented film to decolorize until the colored film satisfies the above level at the time of 500 cycle operation.

Example  And Comparative Example

Example  One

A 300 nm thick WO ₃ layer was deposited on a 250 nm thick ITO / PET laminate using a sputtering method (process pressure 15 mTorr, deposition power 200 W, and deposition time 30 min). Specifically, a WO ₃ layer was formed on one side of the ITO film by winding the film from the roll on which the laminate film was wound using a roll-to-roll apparatus. Then, lithium ion (Li ⁺ ) was inserted into WO ₃ of the ITO / WO ₃ laminate at 10 ^-6 Torr and 640 ° C using a thermal evaporation desposition method to color the WO ₃ layer . At this time, the heat and evaporation, the time is 10 seconds to perform, the Li doping amount is ^{2.0363 × 10 -7 (mol / cm} 2).

Then, the ITO / WO ₃ laminate was laminated with a PB / ITO / PET laminate through a gel polymer electrolyte (GPE) having a thickness of 150 nm to prepare electrochromic films of PET / ITO / WO ₃ / GPE / PB / ITO / A film was prepared. Thus, the electrochromic film had a relatively low translucency (colored state) before actual driving. The PB layer was formed by coating a coating solution containing 30 wt% Prussian blue particles having a diameter of 20 nm, 65 wt% ethanol, and 5 wt% TEOS (Tetraethoxysilane) on ITO using a bar coater, Lt; / RTI &gt; for 5 minutes. The thickness of the PB layer is 250 nm.

The transmittance, the amount of drive charge, and the discoloration rate of the film were observed while applying a decoloring and coloring voltage of ± 2 V per cycle for 50 seconds each. The results are shown in Table 1.

Example  2

An electrochromic film having the same structure was prepared in the same manner as in Example 1, except that the time during which the thermal evaporation was performed was 20 seconds (lithium doping amount: 3.1090 × 10 ^-7 (mol / cm ² )).

Example  3

An electrochromic film having the same structure was prepared in the same manner as in Example 1, except that the time during which thermal evaporation was performed was 30 seconds (lithium doping amount was 4.1090 × 10 ^-7 (mol / cm ² )).

Comparative Example  One

An electrochromic device having the same lamination structure as in Example 1 was prepared in the same manner as in Example 1 except that the process of inserting lithium ions by thermal evaporation was omitted.

Thereafter, a voltage of-5 V was applied to the PB / ITO side of the film for 3 minutes to discolor the PB. As a result, the electrochromic film had a relatively high light transmittance before actual driving. The transmittance, the amount of drive charge, and the discoloration rate were observed while applying the same coloring and decoloring voltages of the same size to the film at the same time intervals. The results are shown in Table 1.

	Lithium Doping Time by Thermal Deposition	Driving charge amount (mC)		Transmittance (%, 500 cycles)		Color change rate (second, 500 cycles)
		1 cycle	50 cycles	coloring	decolorization	coloring	decolorization
Comparative Example 1	0	148	14	51	68	16	16
Example 1	10 seconds	250	50	40	70	15	18
Example 2	20 seconds	285	300	25	70	15	19
Example 3	30 seconds	302	301	24	70	19	17

From Table 1, it can be seen that as the drive time elapses, the amount of decrease in the amount of drive charge and the adherence / discoloration transmittance observed in the comparative film is larger than in the Examples. This means that the long-term driving durability of the film produced according to the embodiment is superior to that of the comparative example.

Claims (11)

1. A method of manufacturing an electrochromic device for sequentially positioning an electrolyte layer and an ion storage layer on an electrochromic layer comprising a reducing electrochromic material,

   Inserting a monovalent cation into the electrochromic layer before placing the electrolyte layer on the electrochromic layer.
2. The method of manufacturing an electrochromic device according to claim 1, wherein a monovalent cation is inserted into the electrochromic layer by deposition.
3. 3. The method of claim 2, wherein monovalent cations are inserted into the electrochromic layer by thermal evaporation desposition,

   Wherein the thermal evaporation is performed at a pressure of 10 mTorr or less and a temperature of 180 DEG C or more.
4. The electrochromic device according to claim 3, wherein the monovalent cation to be inserted into the electrochromic layer is Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ or Cs ⁺ .
5. The electrochromic device according to claim 1, wherein the electrochromic layer comprises an oxide of at least one selected from the group consisting of Ti, Nb, Mo, Ta and W.
6. 6. The method of manufacturing an electrochromic device according to claim 5, further comprising the step of forming a electrochromic layer on a conductive substrate using a roll-to-roll equipment.
7. 7. The method of claim 6, further comprising: releasing the conductive substrate from the roll-to-roll equipment; And forming an electrochromic layer on the electroconductive substrate by a vapor deposition method.
8. 8. The method of manufacturing a semiconductor device according to claim 7, wherein the electrochromic layer is formed on the electroconductive substrate by sputtering deposition,

   Wherein the sputtering deposition is performed under a pressure of 1 to 100 mTorr and a power of 50 to 500 W.
9. The method of claim 1, wherein the electrolyte layer has a gel polymer electrolyte formed from a composition comprising a metal salt capable of providing the same kind of cation as the monovalent cation inserted in the electrochromic layer, an organic solvent, and a crosslinkable monomer A method of manufacturing an electrochromic device.
10. 2. The method of claim 1, wherein the ion storage layer is a porous layer formed from a coating composition comprising electrochromic particles.
11. 11. The method of claim 10, wherein at least one metal oxide particle selected from Cr, Mn, Fe, Co, Ni, Rh, and Ir; Or prussian blue particles is coated on a second conductive base material and then heat-treated to form the ion storage layer.