WO2019054720A1 - Procédé de fabrication de dispositif électrochromique - Google Patents

Procédé de fabrication de dispositif électrochromique Download PDF

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Publication number
WO2019054720A1
WO2019054720A1 PCT/KR2018/010599 KR2018010599W WO2019054720A1 WO 2019054720 A1 WO2019054720 A1 WO 2019054720A1 KR 2018010599 W KR2018010599 W KR 2018010599W WO 2019054720 A1 WO2019054720 A1 WO 2019054720A1
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Prior art keywords
layer
electrochromic
electrochromic layer
ion storage
manufacturing
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PCT/KR2018/010599
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English (en)
Korean (ko)
Inventor
김용찬
김기환
손정우
조필성
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180106524A external-priority patent/KR102118358B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880058151.9A priority Critical patent/CN111095094B/zh
Priority to EP18856359.7A priority patent/EP3686666B1/fr
Priority to US16/645,728 priority patent/US11680309B2/en
Publication of WO2019054720A1 publication Critical patent/WO2019054720A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details

Definitions

  • 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.
  • 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.
  • WO 3 transparent in itself but is colored blue when subjected to a reduction reaction
  • 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.
  • PB Prussian blue
  • 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).
  • 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.
  • a decoloring (reduction) treatment Such an operation is called a so-called initialization operation.
  • 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.
  • One object of the present invention is to provide an electrochromic device improved in driving durability and a method of manufacturing the same.
  • the present application relates to a method of manufacturing an electrochromic device.
  • 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.
  • 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.
  • 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.
  • the insertion of monovalent cations to the electrochromic layer can be accomplished by a dry process.
  • the insertion of monovalent cations to the electrochromic layer can be performed by deposition.
  • the electrochromic layer has an excellent adhesion to the adjacent layer and a separate cleaning step is not required.
  • the monovalent cation insertion to the electrochromic layer can be accomplished by thermal evaporation or thermal evaporation deposition.
  • 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.
  • 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.
  • the thermal evaporation that is, the step of inserting monovalent cations
  • a separate layer composed of a source of monovalent cations is not formed.
  • the thermal evaporation process of the present application may be such that no separate lithium layer is formed on the electrochromic layer.
  • a metal layer such as a lithium layer
  • cell performance may be deteriorated.
  • 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.
  • 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.
  • the thermal evaporation may be performed under a temperature condition where the melting point of the metal ion to be inserted is considered.
  • thermal evaporation can be performed at a temperature above the melting point of the source metal of monovalent cations.
  • 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.
  • the thermal evaporation may be performed at a temperature of about 500 to 700 ⁇ ⁇ .
  • the time for which the abnormal thermal evaporation deposition satisfying the above conditions is performed is not limited.
  • thermal evaporation may be performed for a few seconds to several minutes under the above-described pressure and temperature conditions.
  • 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.
  • 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.
  • 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.
  • the charge quantity can be measured by a known method such as potential step chronoamperometry (PSCA) using a potentiostat device.
  • PSCA potential step chronoamperometry
  • the form in which the inserted monovalent cation exists in the electrochromic layer may include all of the following cases.
  • 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.
  • the electrochromic layer includes a reducing electrochromic material.
  • the reductive electrochromic material may be a material that undergoes coloration when subjected to a reduction reaction.
  • the electrochromic layer may have a discolored state, that is, a colored state.
  • the electrochromic layer may comprise a reducing metal oxide that may be formed by a deposition method.
  • 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.
  • the electrochromic layer may be formed by a dry coating method, for example, a vapor deposition method.
  • 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.
  • 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.
  • 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 .
  • 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.
  • the electrochromic layer may be formed by sputtering deposition.
  • the process conditions of the sputtering deposition are not particularly limited.
  • 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.
  • 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.
  • the flow rate of argon and oxygen gas to be used is not particularly limited.
  • the sputtering deposition under the above conditions can be performed within a range of several minutes to several hours.
  • the electrochromic layer may be formed on a conductive substrate or a release substrate.
  • 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.
  • 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 .
  • the electrochromic layer may be formed by a roll-to-roll method.
  • 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.
  • the roll-to-roll method it is advantageous in securing productivity and fairness.
  • the insertion of the monovalent cations can be effected on a laminate moving along a predetermined path in a roll-to-roll fashion.
  • 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.
  • the thickness of the electrochromic layer is not particularly limited.
  • the thickness of the electrochromic layer may be 1 ⁇ ⁇ 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.
  • 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.
  • the conductive substrate may have a thickness in the range of, for example, 50 nm to 400 nm.
  • the conductive substrate may comprise a transparent conductive compound, a metal mesh, or an oxide / metal / oxide (OMO).
  • OMO oxide / metal / oxide
  • 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.
  • the materials listed above do not limit the material of the transparent conductive oxide.
  • the metal mesh may have a lattice shape comprising Ag, Cu, Al, Mg, Au, Pt, W, Mo, Ti, Ni or alloys thereof.
  • the materials usable for the metal mesh are not limited to the metal materials listed above.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrolyte layer may be a gel polymer electrolyte (GPE).
  • GPE gel polymer electrolyte
  • 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.
  • 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.
  • the gel polymer electrolyte layer may be formed from a crosslinkable monomer-containing composition capable of forming a polymer matrix upon crosslinking.
  • 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 ⁇ ⁇ or more, and the upper limit may be about 200 ⁇ ⁇ or less, about 100 ⁇ ⁇ or less, Or about 10 ⁇ or less.
  • the kind of the crosslinkable monomer is not particularly limited.
  • 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.
  • 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.
  • a carbonate compound may be used as the organic solvent. Since the carbonate compound has a high dielectric constant, the conductivity of the electrolyte ion can be increased.
  • the carbonate compound for example, propylene carbonate (EC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or ethylmethyl carbonate (EMC) may be used.
  • 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.
  • 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.
  • 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.
  • the ion storage layer may be formed by a wet coating method.
  • 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.
  • the substrate to which the coating composition is applied may be a release type substrate or a conductive substrate.
  • 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.
  • 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.
  • water or alcohol may be used as the organic solvent.
  • 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.
  • the heat treatment may be performed at a temperature of about 200 ⁇ ⁇ 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.
  • the ion storage layer when the ion storage layer is formed by a wet coating method, the ion storage layer may be a porous layer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • GPE gel polymer electrolyte
  • 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 > for 5 minutes.
  • the thickness of the PB layer is 250 nm.
  • 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 )).
  • 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 )).
  • 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.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un dispositif électrochromique. Le procédé de fabrication selon la présente invention permet de fabriquer un dispositif par insertion, à l'avance, d'un cation monovalent dans une couche électrochromique réductrice au moyen d'un procédé à sec, puis par stratification de la couche électrochromique colorée, d'une couche d'électrolyte et d'une couche de stockage d'ions contenant une substance chromique oxydante, qui est elle-même dans un état coloré. Ainsi, la présente invention permet d'améliorer la durabilité de fonctionnement d'un dispositif électrochromique.
PCT/KR2018/010599 2017-09-18 2018-09-11 Procédé de fabrication de dispositif électrochromique WO2019054720A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880058151.9A CN111095094B (zh) 2017-09-18 2018-09-11 用于制备电致变色装置的方法
EP18856359.7A EP3686666B1 (fr) 2017-09-18 2018-09-11 Procédé de fabrication de dispositif électrochromique
US16/645,728 US11680309B2 (en) 2017-09-18 2018-09-11 Method for preparing an electrochromic device

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