WO2017155295A1 - Dispositif électrochromique - Google Patents

Dispositif électrochromique Download PDF

Info

Publication number
WO2017155295A1
WO2017155295A1 PCT/KR2017/002491 KR2017002491W WO2017155295A1 WO 2017155295 A1 WO2017155295 A1 WO 2017155295A1 KR 2017002491 W KR2017002491 W KR 2017002491W WO 2017155295 A1 WO2017155295 A1 WO 2017155295A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrochromic
layer
layers
density
different densities
Prior art date
Application number
PCT/KR2017/002491
Other languages
English (en)
Korean (ko)
Inventor
강수희
장성호
김충완
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170028748A external-priority patent/KR102010753B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780004513.1A priority Critical patent/CN108369363B/zh
Priority to US15/774,773 priority patent/US10877348B2/en
Publication of WO2017155295A1 publication Critical patent/WO2017155295A1/fr

Links

Images

Classifications

    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for
    • G02F2001/1536—Constructional details structural features not otherwise provided for additional, e.g. protective, layer inside the cell

Definitions

  • the present application relates to the use of electrochromic devices and electrochromic devices.
  • Electrochromism refers to a phenomenon in which optical properties such as color or transmittance of an electrochromic active material change depending on an electrochemical oxidation and reduction reaction of a material. Electrochromic device using this phenomenon can be manufactured in a large area of the device at a low cost, and because it has a low power consumption, it can be used in various fields such as smart windows, smart mirrors, electronic paper (Patent Document 1: Korean Patent Publication No. 2008-0051280).
  • electrochromic material examples include transition metal oxides.
  • WO 3 , MoO 3 , TiO 2 , and the like may be exemplified as the coloring material by reduction
  • LiNiOx, NIOx, V 2 O 5 , IrO 2 , and the like may be exemplified as the coloring material by oxidation.
  • the electrochromic material may be thinned using sputter vacuum equipment.
  • the vacuum deposition method has a high process cost and maintenance cost, and a thin film of several hundred nm thickness is required for stable driving of the electrochromic device, but it is difficult to apply to mass production due to the low deposition rate.
  • there is a method of coating an electrochromic material there is a method of coating an electrochromic material. The coating method is simpler than the vacuum deposition method, and thus, the process cost is reduced, but additional processes such as treatment treatment may be required due to the reduction in adhesion between the coating layer and the substrate.
  • the problem to be solved by the present application is to increase the productivity of the electrochromic device and to solve and complement the problem of process stability due to the material, to provide an electrochromic device with improved productivity, electrochromic speed and durability and a manufacturing method thereof It is.
  • the present application relates to an electrochromic device.
  • the electrochromic device of the present application may sequentially include a first electrode layer, a composite electrochromic layer, an electrolyte layer, an ion storage layer, and a second electrode layer.
  • the composite electrochromic layer may include a stacked structure of a plurality of electrochromic layers. At least two electrochromic layers of the plurality of electrochromic layers may have different densities from each other. Among the two electrochromic layers having different densities from each other, a higher density electrochromic layer may be disposed adjacent to the first electrode layer than the lower density electrochromic layer.
  • the first and second electrode layers may be provided on the first and second substrates, respectively.
  • the electrochromic device of the present application may be implemented through a laminated structure of relatively small thicknesses of electrochromic layers, thereby increasing productivity.
  • the electrochromic device of the present application prevents ions (eg, Li + ions) in the electrolyte layer from penetrating into the electrode layer through the arrangement of a plurality of electrochromic layers having different densities from each other. Deterioration due to side reactions of the electrode layer material (eg, ITO) can be reduced, thereby exhibiting excellent electrochromic speed and durability.
  • an electrochromic device may include a first substrate 10, a first electrode layer 11, a composite electrochromic layer 12, an electrolyte layer 3, and an ion storage layer. 22, the second electrode layer 21, and the second substrate 20 may be sequentially included.
  • the composite electrochromic layer 12 may include at least two electrochromic layers 121 and 122 having different densities from each other, and a higher density of the first electrochromic layer 121 may include a second electrochromic layer having a lower density. It may be disposed closer to the first electrode layer 11 than to the color change layer.
  • the higher density of the first electrochromic layer 121 is adjacent to the first electrode layer 11, and the lower density of the second electrochromic layer 122 is the electrolyte layer 3. Adjacent to).
  • an electrode layer adjacent to the composite electrochromic layer may be referred to as a first electrode layer, and an electrode layer adjacent to the ion storage layer may be referred to as a second electrode layer.
  • the first and second electrode layers may perform a function of supplying charge to the composite electrochromic layer or the ion storage layer.
  • the first electrode layer may be referred to as an electrode, for example, an active electrode, which is electrochromic in the electrochromic device while adjacent to the composite electrochromic layer.
  • the second electrode layer may be referred to as an electrode, for example, a counter electrode, adjacent to the ion storage layer and capable of receiving hydrogen or lithium ions desorbed from the active electrode.
  • both the first electrode layer and the second electrode layer may be active electrodes and function as counter electrodes.
  • the first and second electrode layers may each comprise a transparent conductive material.
  • each of the first and second electrode layers may include at least one of a transparent conductive oxide, a conductive polymer, a silver nanowire, or a metal mesh.
  • the transparent conductive oxide includes indium tin oxide (ITO), fluor doped tin oxide (FTO), aluminum doped zinc oxide (AZO), gallium doped zinc oxide (GZO), antimony doped tin oxide (ATO), IZO (Indium doped Zinc Oxide), Niobium doped Titanium Oxide (NTO), ZnO, or CTO may be used, but is not limited thereto.
  • the first and second electrode layers may be formed in a structure in which two or more of the above-mentioned transparent conductive oxides are stacked.
  • the first or second electrode layer can be produced by, for example, forming an electrode material containing transparent conductive oxide particles in a thin film form on a transparent glass substrate through a process such as sputtering or digital printing.
  • the first or second electrode layer can be designed to have low thickness and sheet resistance and high transmittance. As the sheet resistance of the first or second electrode layer is lower, the coloring and decolorization conversion time of the electrochromic device tends to decrease. In consideration of this point, the physical properties of the first or second electrode layer can be appropriately adjusted.
  • the thickness of the first or second electrode layer can be 1 nm to 500 nm.
  • the voltage applied to the first or second electrode layer through an external circuit can be appropriately adjusted within a range that does not impair the purpose of the present application.
  • the voltage applied to the first or second electrode layer through the external circuit can be appropriately adjusted.
  • the voltage applied to the first or second electrode layer through an external circuit may be -5 V to + 5 V, but is not limited thereto.
  • the voltages at the time of coloring and decoloring may be the same or different, which may be appropriately adjusted as necessary.
  • the voltage may be applied by an AC power source, and a power supply device or a method of applying the voltage may be appropriately selected by those skilled in the art.
  • the electrochromic device of the present application may further include first and second substrates disposed on one surface of the first and second electrode layers, respectively.
  • the first and second substrates may be glass substrates or polymer substrates, respectively.
  • the first and second substrates may be any one selected from the group consisting of glass, glass fiber, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polyimide, and combinations thereof.
  • the first substrate may be a glass substrate and the second substrate may be a polymer substrate.
  • the composite electrochromic layer can have a stacked structure of a plurality of electrochromic layers.
  • the stacked structure of the plurality of electrochromic layers may refer to a stacked structure of at least two electrochromic layers.
  • the electrochromic layer when not limited to “composite” or “plural”, the electrochromic layer may refer to one electrochromic layer formed independently.
  • the composite electrochromic layer may have a stacked structure of two, three, four, five, or more electrochromic layers as needed.
  • At least two electrochromic layers of the plurality of electrochromic layers may have different densities from each other.
  • a higher density electrochromic layer may be disposed closer to the first electrode layer than the lower density electrochromic layer.
  • This arrangement prevents ions (eg Li + ions) in the electrolyte layer from penetrating into the electrode layer, thereby reducing degradation due to side reactions of the ions in the electrolyte layer and the electrode layer material (eg ITO). Can exhibit excellent electrochromic speed and durability.
  • a higher density electrochromic layer may be disposed adjacent to the first electrode layer, and the lower density The layer may be disposed adjacent to the electrolyte layer.
  • the composite electrochromic layer has a laminated structure of three or more electrochromic layers having different densities from each other, the highest electrochromic layer is adjacent to the first electrode layer, and the lowest electrochromic is made.
  • the layer can be disposed adjacent to the electrolyte layer.
  • the lower the density of the electrochromic layers from the first electrode layer side toward the electrolyte layer side may be disposed.
  • the plurality of electrochromic layers may be disposed such that at least two electrochromic layers having different densities are adjacent to each other. Therefore, according to the electrochromic device of the present application, at least two electrochromic layers having different densities from each other may be driven to be adjacent to each other.
  • the plurality of electrochromic layers may be, for example, at least two electrochromic layers having different densities from each other directly stacked on each other.
  • a and B are directly stacked on each other may mean that A and B are laminated to each other without the presence of an intermediate layer such as an adhesive layer or an adhesive layer.
  • Directly stacking the two or more electrochromic layers with each other may be performed, for example, by depositing or coating another electrochromic layer on one electrochromic layer.
  • the density difference between two electrochromic layers having different densities may be appropriately selected in consideration of the purpose of the present application.
  • the density difference is 0.1 g / cm 3 , 0.2 g / cm 3 , 0.3 g / cm 3 , 0.4 g / cm 3 Or 0.5 g / cm 3 or more.
  • the upper limit of the density difference may be 3.0 g / cm 3 or less.
  • the density of each of the two electrochromic layers having different densities from each other may be appropriately selected in consideration of the purpose of the present application.
  • the higher density of the electrochromic layer among the two electrochromic layers having different densities may be 5.0 g / cm 3 to 8.0 g / cm 3 .
  • the denser electrochromic layer has a density of at least 5.0 g / cm 3, at least 5.25 g / cm 3, at least 5.5 g / cm 3, at least 5.75 g / cm 3, at least 6 g / cm 3, or 6.25 g.
  • the density of the lower electrochromic layer may be 3.0 g / cm 3 to 7.0 g / cm 3 .
  • the lower density electrochromic layer has a density of at least 3.0 g / cm 3, at least 3.5 g / cm 3, at least 4.0 g / cm 3, at least 4.5 g / cm 3, at least 5.5 g / cm 3, or 5.5 g.
  • / cm 3 or more may be 7.0 g / cm 3 or less, 6.5 g / cm 3 or less, or 6.0 g / cm 3 or less.
  • productivity may be increased, and it may be advantageous in terms of implementing an electrochromic device having excellent electrochromic speed and durability.
  • the thickness of the individual electrochromic layers included in the composite electrochromic layer may be appropriately selected in consideration of the purpose of the present application.
  • the thickness of the individual electrochromic layers can each be between 10 nm and 800 nm.
  • the thickness of the electrochromic layer having a higher density among the two electrochromic layers having different densities may be 10 nm to 800 nm, and the thickness of the lower density electrochromic layer may be 10 nm to 800 nm.
  • the higher density of the electrochromic layer may be 10 nm or more, 20 nm or more, 30 nm or more, 60 nm or more, or 90 nm or more, and 400 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less.
  • the lower density of the electrochromic layer may be 10 nm or more, 50 nm or more, 100 nm or more, or 150 nm or more, and 400 nm or less, 300 nm or less, or 200 nm or less.
  • the entire thickness of the composite electrochromic layer may be 20 nm to 810 nm.
  • the total thickness of the composite electrochromic layer may be 20 nm or more, 60 nm or more, 100 nm or more, 140 nm or more, or 180 nm or more, and may be 810 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, or 300 nm or less.
  • productivity may be increased, and an electrochromic device having excellent electrochromic speed and durability may be advantageous in terms of implementing the electrochromic device.
  • At least two electrochromic layers having different densities may be implemented through different physical structures.
  • the electrochromic layer of any one of at least two electrochromic layers having different densities may be a porous film.
  • the lower density electrochromic layer among the at least two electrochromic layers having different densities may be a porous film as compared to the higher density electrochromic layer.
  • the porous film may mean a film having a porous structure, that is, a film having a plurality of porosity (Porosity) in the interior or surface of the film.
  • A is a porous film as compared to B, which may mean that A includes more voids than B.
  • the plurality of electrochromic layers may be, for example, at least two electrochromic layers having different densities from each other may include an electrochromic material.
  • Electrochromism is a phenomenon in which the color is reversibly changed in response to an electrical signal. Electrochromism may be caused by an insertion / extraction process of electrons and ions (H + , Li +, etc.) in the electrochromic material. Electrochromic materials can be classified into reducing electrochromic materials that are reversibly colored by ion insertion and oxidative electrochromic materials that are reversibly colored by ion extraction.
  • electrochromic material a metal oxide electrochromic material, a metal complex, an organic electrochromic material, or a conductive polymer electrochromic material may be used.
  • metal oxide electrochromic materials include tungsten (W), titanium (Ti), vanadium (V), molybdenum (Mo), niobium (Nb), chromium (Cr), manganese (Mn), and tantalum (Ta). At least one of metal oxides of iron (Fe), nickel (Ni), cobalt (Co), iridium (Ir), and lithium nickel (LiNi) may be used.
  • Metal oxides such as tungsten (W), titanium (Ti), vanadium (V), molybdenum (Mo), and niobium (Nb) may be classified as reducing electrochromic materials, vanadium (V), chromium (Cr), Manganese (Mn), tantalum (Ta), iron (Fe), nickel (Ni), cobalt (Co), iridium (Ir) or lithium nickel (LiNi) may be classified as oxidative electrochromic materials.
  • metal complex for example, Prussian blue, Phthalocyanines or Bismuth may be used.
  • organic electrochromic material for example, viologen or quinone may be used.
  • Examples of the conductive polymer electrochromic material include polythiophene, polyaniline, polypyrrole, polyanthracene, polyfluorene, polycarbazole, polyphenylene One or more of polyphenylenevinylene and derivatives thereof can be used.
  • the plurality of electrochromic layers for example, at least two electrochromic layers having different densities from each other may include the same kind of electrochromic material.
  • two or more electrochromic layers having different densities may include tungsten oxide (WOx).
  • the electrochromic device of the present application implements different density of two or more electrochromic layers including the same kind of electrochromic material, thereby solving and supplementing the problem of increased productivity of the electrochromic device and process stability due to materials. can do.
  • the ion storage layer may serve to receive and recharge the charge of ions necessary to cause the electrochromic layer to discolor.
  • the ion storage layer may comprise a conductive material complementary to the electrochromic layer.
  • the ion storage layer may comprise an oxidative conductive material when the composite electrochromic layer comprises a reducing electrochromic material.
  • the ion storage layer may comprise a reducing conductive material when the composite electrochromic layer comprises an oxidizing electrochromic material.
  • the conductive material included in the ion storage layer may be an electrochromic material. If the composite electrochromic layer comprises a reducing electrochromic material, the ion storage layer may comprise an oxidizing electrochromic material, and if the composite electrochromic layer comprises an oxidizing electrochromic material, the ion storage layer comprises a reducing electrochromic material. can do. According to one embodiment of the present application, when tungsten oxide (WO 3 ) is used in the composite electrochromic layer, lithium nickel oxide (LiNixOy) may be used in the ion storage layer.
  • tungsten oxide WO 3
  • LiNixOy lithium nickel oxide
  • the ion storage layer may comprise a suitable conductive material, for example conductive material such as conductive graphite, regardless of whether the composite electrochromic layer contains a reducing color change material or an oxidizing color change material.
  • the thickness of the ion storage layer may be appropriately selected within a range that does not impair the purpose of the present application.
  • the thickness of the ion storage layer may be 20 nm to 810 nm.
  • the electrolyte layer may comprise an electrolyte salt.
  • the electrolyte layer may be any one selected from the group consisting of a liquid electrolyte, a gel electrolyte, a solid electrolyte, a polymer electrolyte, and a gel polymer electrolyte in which an electrolyte salt is dissolved, and in the case of a liquid electrolyte, an electrolyte salt may be dissolved in a solvent. have.
  • the electrolyte may be a gel polymer electrolyte.
  • the electrolyte salt may be an organic electrolyte salt or an inorganic electrolyte salt. More specifically, the electrolyte salt may include a lithium salt, potassium salt, sodium salt or ammonium salt, for example, the electrolyte salt is n-Bu 4 NClO 4 , n-Bu 4 NPF 6 , NaBF 4 , LiClO 4 , Any one selected from the group consisting of LiPF 6 , LiBF 4 , LiN (SO 2 C 2 F 5 ) 2 , LiCF 3 SO 3 , C 2 F 6 LiNO 4 S 2 , K 4 Fe (CN) 6, and combinations thereof Can be.
  • the solvent may be applied as long as it is a non-aqueous solvent, and specifically, dichloromethane, chloroform, acetonitrile, ethylene carbonate (EC), propylene carbonate (PC), tetrahydrofuran (THF), butylene carbonate, and combinations thereof. It may be any one selected from the group consisting of.
  • the thickness of the electrolyte layer may be appropriately selected within a range that does not impair the purpose of the present application.
  • the thickness of the electrolyte layer may be 400 nm to 2000 nm.
  • the thickness of the electrolyte layer satisfies the above range, it is possible to provide an electrochromic device having improved electrochromic speed and stability.
  • the present application also relates to a method of manufacturing an electrochromic device.
  • the manufacturing method may be a manufacturing method of the electrochromic device described above.
  • the manufacturing method may include sequentially stacking a composite electrochromic layer, an electrolyte layer, an ion storage layer, and a second electrode layer on the first electrode layer.
  • the composite electrochromic layer includes a plurality of electrochromic layers, wherein at least two electrochromic layers of the plurality of electrochromic layers have different densities from each other, and among the two electrochromic layers having different densities from each other.
  • the higher density electrochromic layer may be stacked so as to be adjacent to the first electrode layer as compared to the lower density electrochromic layer.
  • the details of the first electrode layer, the composite electrochromic layer, the electrolyte layer, the ion storage layer and the second electrode layer may be the same as described in the items of the electrochromic device.
  • the interlayer lamination method can be made by appropriately selecting a known method.
  • sputtering, sol-gel, e-beam evaporation, pulsed laser deposition, chemical vapor deposition, spin coating, or Each layer can be formed using any of dip coating methods.
  • differently controlling the density of the two or more electrochromic layers may be performed by laminating one electrochromic layer in the form of a porous film as compared to another adjacent electrochromic layer. Details of the porous film may be the same as described in the item of the electrochromic device.
  • laminating the electrochromic layer in the form of a porous film may be achieved by applying a sputtering process in order to deposit the electrochromic layer, but adjusting process pressure conditions or an E-beam evaporation process. By applying but adjusting the gas conditions. Process pressure conditions in the sputter process or gas conditions in the electron beam deposition process may be appropriately selected depending on the density to be implemented.
  • the higher the process pressure the less the density of the electrochromic layer tends to decrease.
  • the density of the electrochromic layer tends to decrease as the process pressure increases through gas injection.
  • the source of the sputtering process is a solid solid of the metal component
  • the source of the electron beam deposition process is a solid in the form of Granule
  • the electrochromic device of the present application has the effect of improving the electrochromic speed and stability.
  • Such electrochromic devices may be usefully used in various devices such as smart windows, smart mirrors, displays, electronic paper, and active camouflage.
  • the manner of configuring such a device is not particularly limited and a conventional manner may be applied as long as the electrochromic device of the present application is applied.
  • the present application can provide an electrochromic device having increased productivity and improved electrochromic speed and durability.
  • electrochromic devices may be usefully used in various devices such as smart windows, smart mirrors, displays, electronic paper, and active camouflage.
  • FIG. 1 exemplarily shows an electrochromic device according to an embodiment of the present application.
  • FIG. 6 is a coloration and decolorization image at 750 cycles of Example 1.
  • FIG. 7 is a coloration and decolorization image at 750 cycles of Example 2.
  • FIG. 8 is a color image of 400 cycles of Example 3.
  • 15 to 16 are graphs of the charge amounts of Example 2 and Comparative Example 2, respectively.
  • FIG. 17 is a color image of 50 cycles of Comparative Example 2.
  • FIG. 18 is a graph showing transmittance and charge amount of Comparative Example 2.
  • the density of the electrochromic layer thin film was measured for 1 second every 0.002 degrees from 2theta 0.2 degree to 2.4 degree using X-ray reflectometry (XRR) analysis.
  • XRR X-ray reflectometry
  • Example 1 (Stack: Glass / ITO / WOx (One)/ WOx (2)/ GPE Of LiNixOy / ITO / PET film)
  • the first electrochromic layer 121 was formed by providing a thin film having a thickness of about 30 nm.
  • WOx (tungsten oxide) was formed on the first electrochromic layer 121 by electron beam evaporation at a deposition rate of 6.03 kV at a high voltage of 0.5 nm / sec.
  • a second electrochromic layer 122 was formed.
  • the density of the first electrochromic layer 121 is about 6.3 ⁇ 0.1 g / cm 3 and the density of the second electrochromic layer 122 is about 5.8 ⁇ 0.1 g / cm 3 .
  • LiNixOy After forming a plasma on the LiNiO 2 target by using a DC sputter on the ITO layer laminated on the PET film, and injecting Ar and O 2 Gas into the chamber through a reactive reaction, LiNixOy has a thickness of about 75nm
  • the ion storage layer 22 was formed by being provided as a thin film.
  • the working and counter electrodes are arranged so that the second electrochromic layer 122 and the ion storage layer 21 contact the gel polymer electrolyte 3.
  • the gel polymer electrolyte comprising a mixture of propylene carbonate (PC) and LiClO 4 .
  • Example 2 (Stack: Glass / ITO / WOx (One)/ WOx (2)/ GPE Of LiNixOy / ITO / PET film)
  • the electrochromic color was changed in the same manner as in Example 1, except that the DC sputtering time was doubled to provide a thin film having a thickness of about 60 nm.
  • the device was manufactured.
  • the density of the first electrochromic layer thin film 121 is about 6.3 ⁇ 0.1 g / cm 3
  • the density of the second electrochromic layer thin film 122 is about 5.8 ⁇ 0.1 g / cm 3 .
  • Example 3 (Stack: Glass / ITO / WOx (One)/ WOx (2)/ GPE Of LiNixOy / ITO / PET film)
  • Example 1 the first electrochromic layer thin film 121 was formed in the same manner as in Example 1 except that the DC sputtering time was increased three times to provide a thin film having a thickness of about 90 nm. A color change device was prepared.
  • the density of the first electrochromic layer thin film 121 is about 6.3 ⁇ 0.1 g / cm 3
  • the density of the second electrochromic layer thin film 122 is about 5.8 ⁇ 0.1 g / cm 3 .
  • Comparative example 1 (Stack: Glass / ITO / WOx Of GPE Of LiNixOy / ITO / PET film)
  • Example 1 In manufacturing the working electrode in Example 1, in forming the first electrochromic layer thin film 121, except that the electrochromic layer formed of a single layer structure of a thin film of about 420nm thickness by increasing the DC sputtering time by 14 times Then, an electrochromic device was manufactured in the same manner as in Example 1.
  • the density of the electrochromic layer thin film is about 6.3 ⁇ 0.1 g / cm 3 .
  • Comparative example 2 (Stack: Glass / ITO / WOx (2)/ WOx (One)/ GPE Of LiNixOy / ITO / PET film)
  • a second electrochromic layer 122 having a density of about 5.8 ⁇ 0.1 g / cm 3 is first formed on the ITO electrode layer, and then on the second electrochromic layer 122
  • An electrochromic device was manufactured in the same manner as in Example 2, except that a first electrochromic layer 121 having a density of about 6.3 ⁇ 0.1 g / cm 3 was formed.
  • Comparative Example 1 does not deteriorate after 100 cycles, whereas Examples 1 to 2 do not deteriorate even after 800 cycles, and Example 3 deteriorates up to about 150 cycles. It can be confirmed that the durability is superior to Comparative Example 1.
  • 7 and 8 are colored and decolorized images after driving 750 cycles of the electrochromic devices of Examples 1 and 2, respectively, and FIG. 9 is a colored image after driving 400 cycles for Example 3.
  • FIG. 9 is a colored image after driving 400 cycles for Example 3.
  • 9 to 11 show changes in the amount of charge during discoloration and decoloration with the elapsed time of the electrochromic elements of Examples 1 to 3, respectively.
  • As the amount of charge increases it may mean that Li + ions contribute a lot to coloring, decoloring, or electrochromic color.
  • FIGS. 9 and 11 in Examples 1 and 2, it can be seen that up to about 750 cycles exhibits stable electrochromic properties without a decrease in charge amount.
  • 12 to 14 show changes in transmittance and charge amount during coloration and decoloration according to the number of cycles of the electrochromic devices of Examples 1 to 3, respectively.
  • Example 15 to 16 show changes in charge amount during discoloration and decoloration with elapsed time of the electrochromic devices of Example 2 and Comparative Example 2, respectively.
  • Example 2 shows a stable electrochromic properties without a decrease in the amount of charge over time
  • Comparative Example 2 can be seen that the amount of charge decreases after 50 Cycle.
  • 17 is a coloring image after driving 50 cycles of Comparative Example 2.
  • FIG. 18 shows changes in transmittance and charge amount during coloration and decoloration according to the number of cycles of the electrochromic device of Comparative Example 2.

Landscapes

  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

La présente invention concerne un dispositif électrochromique et un procédé de fabrication du dispositif électrochromique. Elle concerne en outre un dispositif électrochromique qui présente une productivité accrue et de meilleures vitesse et durabilité d'électrochromisme, et un procédé de fabrication du dispositif électrochromique. Le dispositif électrochromique peut être utile dans divers appareils tels qu'une fenêtre intelligente, un miroir intelligent, un écran, un papier électronique et un camouflage adaptatif.
PCT/KR2017/002491 2016-03-08 2017-03-08 Dispositif électrochromique WO2017155295A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201780004513.1A CN108369363B (zh) 2016-03-08 2017-03-08 电致变色装置
US15/774,773 US10877348B2 (en) 2016-03-08 2017-03-08 Electrochromic device

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20160027597 2016-03-08
KR10-2016-0027597 2016-03-08
KR10-2017-0028748 2017-03-07
KR1020170028748A KR102010753B1 (ko) 2016-03-08 2017-03-07 전기변색 소자

Publications (1)

Publication Number Publication Date
WO2017155295A1 true WO2017155295A1 (fr) 2017-09-14

Family

ID=59789633

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/002491 WO2017155295A1 (fr) 2016-03-08 2017-03-08 Dispositif électrochromique

Country Status (1)

Country Link
WO (1) WO2017155295A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108534930A (zh) * 2018-03-23 2018-09-14 京东方科技集团股份有限公司 压力可视化装置及其制备方法、检测设备
CN109683418A (zh) * 2019-01-10 2019-04-26 五邑大学 一种智能窗及其制造方法
CN111880348A (zh) * 2020-08-07 2020-11-03 中国科学院广州能源研究所 一种新型电致变色器件及其制备方法
CN112596318A (zh) * 2020-12-14 2021-04-02 中建材蚌埠玻璃工业设计研究院有限公司 一种电致变色智能玻璃复合薄膜及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303310A (en) * 1978-06-05 1981-12-01 Tokyo Shibaura Denki Kabushiki Kaisha Electrochromic display device
KR20030072123A (ko) * 2002-03-05 2003-09-13 주식회사 엘지이아이 전기변색소자 및 그 제조방법
KR20070047597A (ko) * 2005-11-02 2007-05-07 주식회사 엘지화학 전기변색소자의 전극구조
JP2012098628A (ja) * 2010-11-04 2012-05-24 Canon Inc エレクトロクロミック素子
KR20150076780A (ko) * 2013-12-27 2015-07-07 한국전자통신연구원 전기 변색 소자 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303310A (en) * 1978-06-05 1981-12-01 Tokyo Shibaura Denki Kabushiki Kaisha Electrochromic display device
KR20030072123A (ko) * 2002-03-05 2003-09-13 주식회사 엘지이아이 전기변색소자 및 그 제조방법
KR20070047597A (ko) * 2005-11-02 2007-05-07 주식회사 엘지화학 전기변색소자의 전극구조
JP2012098628A (ja) * 2010-11-04 2012-05-24 Canon Inc エレクトロクロミック素子
KR20150076780A (ko) * 2013-12-27 2015-07-07 한국전자통신연구원 전기 변색 소자 및 그 제조방법

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108534930A (zh) * 2018-03-23 2018-09-14 京东方科技集团股份有限公司 压力可视化装置及其制备方法、检测设备
CN108534930B (zh) * 2018-03-23 2019-12-10 京东方科技集团股份有限公司 压力可视化装置及其制备方法、检测设备
CN109683418A (zh) * 2019-01-10 2019-04-26 五邑大学 一种智能窗及其制造方法
CN111880348A (zh) * 2020-08-07 2020-11-03 中国科学院广州能源研究所 一种新型电致变色器件及其制备方法
CN111880348B (zh) * 2020-08-07 2023-04-28 中国科学院广州能源研究所 一种新型电致变色器件及其制备方法
CN112596318A (zh) * 2020-12-14 2021-04-02 中建材蚌埠玻璃工业设计研究院有限公司 一种电致变色智能玻璃复合薄膜及其制备方法
CN112596318B (zh) * 2020-12-14 2022-09-20 中建材玻璃新材料研究院集团有限公司 一种电致变色智能玻璃复合薄膜及其制备方法

Similar Documents

Publication Publication Date Title
US10877348B2 (en) Electrochromic device
KR102010733B1 (ko) 전기변색 소자
WO2017155295A1 (fr) Dispositif électrochromique
KR102038184B1 (ko) 전기변색소자
EP2555048B1 (fr) Dispositif électrochromique
KR102141635B1 (ko) 전기변색소자
US11099450B2 (en) Electrochromic device
WO2017217710A1 (fr) Dispositif électrochrome
WO2019199011A1 (fr) Film électrochromique
WO2017065472A1 (fr) Élément électrochromique et son procédé de fabrication
KR20190032200A (ko) 전기변색소자의 제조방법
Tang et al. Structure evolution of electrochromic devices from ‘face-to-face’to ‘shoulder-by-shoulder’
WO2019050252A1 (fr) Dispositif de protection de confidentialité destiné à des dispositifs d'affichage permettant une commutation entre un mode grand angle de vision et un mode angle de vision étroit
KR102079142B1 (ko) 전기변색소자
KR102056599B1 (ko) 전기변색소자
KR102010734B1 (ko) 전기변색소자
KR102108562B1 (ko) 전기변색소자
KR102010754B1 (ko) 전기변색소자
KR102101151B1 (ko) 전기변색소자
KR102108553B1 (ko) 전기변색소자
KR102069486B1 (ko) 전기변색소자
WO2017217635A1 (fr) Dispositif électrochromique flexible utilisant une électrode composite en graphène de haute qualité et son procédé de fabrication
KR102071901B1 (ko) 전기변색소자
WO2018199572A1 (fr) Stratifié conducteur et dispositif électrochromique comprenant ce dernier
WO2019054720A1 (fr) Procédé de fabrication de dispositif électrochromique

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17763556

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17763556

Country of ref document: EP

Kind code of ref document: A1