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WO2018199572A1 - Stratifié conducteur et dispositif électrochromique comprenant ce dernier - Google Patents

Stratifié conducteur et dispositif électrochromique comprenant ce dernier Download PDF

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Publication number
WO2018199572A1
WO2018199572A1 PCT/KR2018/004674 KR2018004674W WO2018199572A1 WO 2018199572 A1 WO2018199572 A1 WO 2018199572A1 KR 2018004674 W KR2018004674 W KR 2018004674W WO 2018199572 A1 WO2018199572 A1 WO 2018199572A1
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WIPO (PCT)
Prior art keywords
layer
metal
conductive laminate
conductive
oxide
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PCT/KR2018/004674
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English (en)
Korean (ko)
Inventor
김용찬
장성호
김기환
조필성
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.)
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Priority claimed from KR1020180045421A external-priority patent/KR20180119120A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US16/604,893 priority Critical patent/US20200255723A1/en
Priority to EP18790462.8A priority patent/EP3618082A4/fr
Priority to CN201880027087.8A priority patent/CN110574127A/zh
Priority to JP2019557571A priority patent/JP2020518003A/ja
Publication of WO2018199572A1 publication Critical patent/WO2018199572A1/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
    • G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present application relates to a conductive laminate and an electrochromic device including the same.
  • Electrochromic refers to a phenomenon in which the optical properties of an electrochromic material are changed by an electrochemical oxidation or reduction reaction, and the device using the phenomenon is called an electrochromic device.
  • Electrochromic devices generally include a working electrode, a counter electrode, and an electrolyte, and the optical properties of each electrode may be reversibly changed by an electrochemical reaction.
  • the working electrode or the counter electrode may include a transparent conductive material and an electrochromic material, respectively, in the form of a film.
  • Such electrochromic devices are attracting attention as smart windows, smart mirrors, and other next-generation building window materials because they can manufacture devices with a large area at low cost and have low power consumption.
  • the discoloration rate is slow. This disadvantage is more pronounced when the surface resistance of the transparent conductive electrode is high or when a large area of the electrochromic device is required.
  • One object of the present application is to provide an electrochromic conductive laminate.
  • Another object of the present application is to provide a conductive laminate in which the color change rate is improved.
  • Another object of the present application is to provide a conductive laminate having excellent durability and an improved usable level.
  • Another object of the present application is to provide a conductive laminate in which the permeability control can be made fine.
  • Still another object of the present application is to provide an electrochromic device including the conductive laminate.
  • the present application relates to a conductive laminate.
  • the conductive laminate has a variable transmittance characteristic by electrochromic color.
  • the conductive laminate includes an electrochromic material, and since the optical property may change as a result of electrochromic reaction due to an electrochemical reaction, it may be used as one configuration of an electrochromic device. Electrochromic can occur in one or more layers included in the conductive laminate.
  • the conductive laminate includes a metal oxynitride layer, a metal oxide layer, and a conductive layer.
  • the form in which the said electroconductive laminated body contains each laminated constitution is not specifically limited.
  • the conductive laminate may sequentially include a metal oxynitride layer, a metal oxide layer, and a conductive layer, or may sequentially include a metal oxide layer, a metal oxynitride layer, and a conductive layer.
  • a separate layer may be present between the layers, or one surface of each layer may directly contact each other to form a conductive laminate.
  • the metal oxide layer, the metal oxynitride layer, and the conductive layer may have light transmittance.
  • the term “transmittance” may mean a case where the optical property such as a color change occurring in the electrochromic device is transparent enough to clearly recognize, for example, a state without external factors such as potential application ( And / or in a decolorized state), the light transmittance of the layer may be at least 60% or more. More specifically, the lower limit of the light transmittance of the metal oxide layer, the metal oxynitride layer, and the conductive layer may be 60% or more, 70% or more, or 75% or more, and the upper limit of the light transmittance may be 95% or less, 90% or less, Or 85% or less.
  • the change in the optical properties of the electrochromic device due to electrochromic that is, reversible coloring and decolorization according to the potential application can be sufficiently visible to the user. That is, when it has the said light transmittance in the uncolored state, it is suitable for an electrochromic element.
  • the term "light” in the present application may mean visible light in a wavelength range of 380 nm to 780 nm, and more specifically, visible light in a 550 nm wavelength.
  • the transmittance can be measured using a known haze meter (HM).
  • the metal oxide layer may include an electrochromic material, that is, an electrochromic metal oxide.
  • the metal oxide layer may include a reducing (inorganic) discoloration material in which coloration occurs during the reduction reaction.
  • a reducing (inorganic) discoloration material in which coloration occurs during the reduction reaction.
  • the kind of reducing (inorganic) discoloration material that can be used is not particularly limited, but oxides of Ti, Nb, Mo, Ta, or W may be used.
  • WO 3 , MoO 3 , Nb 2 O 5 , Ta 2 O 5, TiO 2 , or the like can be used.
  • the metal oxide layer may include an oxidative discoloration material that is colored when oxidized.
  • the type of oxidative discoloration material that can be used is not particularly limited, but an oxide of Cr, Mn, Fe, Co, Ni, Rh, or Ir may be used.
  • LiNiOx, IrO 2 , NiO, V 2 O 5 , LixCoO 2, Rh 2 O 3, CrO 3, or the like may be used.
  • the thickness of the metal oxide layer may range from 50 nm to 450 nm.
  • the method for forming the metal oxide layer is not particularly limited.
  • the layer may be formed using various kinds of known deposition methods.
  • the metal oxynitride layer may include an oxynitride containing two or more metals at the same time.
  • the metal oxynitride layer may have an oxynitride including two or more metals selected from Ti, Nb, Mo, Ta and W simultaneously.
  • the metal oxynitride layer may include Mo and Ti at the same time.
  • nitrides, oxides or oxynitrides containing only Mo are poor in adhesion to adjacent thin films, and nitrides, oxides or oxynitrides containing only Ti are poor in durability, such as decomposing upon application of potential.
  • nitrides or oxynitrides containing any one of the metals listed above, such as Ti alone or Mo only are for example 40% or less, 35% or less or 30% or less, even when no potential is applied. Since it has low light transmittance, such as having a visible light transmittance of, it is not suitable for use as an electrochromic film member requiring transparency when bleached. In addition, in the case of using a material having a low transmittance as described above, it is difficult for the user to see a clear change in the optical properties of coloring and discoloration required in the electrochromic device.
  • the metal oxynitride included in the metal oxynitride layer may be represented by the following formula (1).
  • a means an element content ratio of Mo
  • b means an element content ratio of Ti
  • x means an element content ratio of O
  • y means an element content ratio of N
  • the term "element content ratio" in the present application may be atomic%, and may be measured by X-ray photoelectron spectroscopy (XPS). When the element content ratio (a / b) is satisfied, a metal oxynitride layer excellent in adhesion as well as other layer constitutions may be provided.
  • the metal oxynitride layer may have a light transmittance of 60% or more.
  • the element content ratio (y / x) is not satisfied, as the oxynitride layer has a very low light transmittance (transparency), such as having a light transmittance of 40% or less or 35% or less, the oxynitride layer Cannot be used as a member for electrochromic elements.
  • the thin film density ( ⁇ ) of the metal oxynitride layer may be 15 g / cm 3 or less.
  • the lower limit of the thin film density ( ⁇ ) value may be 0.5 g / cm 3 or more, 0.7 g / cm 3 or more, or 1 g / cm 3 or more
  • the upper limit of the thin film density ( ⁇ ) value is 13 or less g / cm 3 or 10 g / cm 3 or less.
  • Thin film density can be measured by X-ray reflectivity (XRR).
  • the thickness of the metal oxynitride layer may be 150 nm or less.
  • the metal oxynitride layer may have a thickness of 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, or 100 nm or less.
  • the lower limit of the thickness of the metal oxynitride layer is not particularly limited, but may be, for example, 10 nm or more, 20 nm or more, or 30 nm or more. If it is less than 10 nm, the film stability is not good.
  • the visible light refractive index of the metal oxynitride layer may be in the range of 1.5 to 3.0 or 1.8 to 2.8.
  • appropriate light transmittance may be implemented in the conductive laminate.
  • the method for forming the metal oxynitride layer is not particularly limited.
  • the layer may be formed using various kinds of known deposition methods.
  • monovalent cations may be present in at least one or more layers of the layer structures constituting the conductive laminate.
  • the monovalent cation may be present in either of the metal oxynitride layer and the metal oxide layer, or the monovalent cation may be present in both the metal oxynitride layer and the metal oxide layer.
  • the presence of a monovalent cation in any layer of the conductive laminate for example, when the monovalent cation is included (inserted) in each layer in the form of an ion such as Li + , and the inserted monovalent
  • the cation may be used to encompass a case where the cation is chemically bonded to the metal oxynitride or the metal oxide and included in each layer.
  • the insertion of the monovalent cation may be made before the fabrication of the electrochromic device (formed by laminating the electrolyte layer and the conductive laminate).
  • the monovalent cation may be a cation of an element different from the metal contained in the metal oxynitride layer or the metal oxide layer.
  • the monovalent cation may be, for example, H + , Li + , Na + , K + , Rb + or Cs + .
  • the monovalent cation can also be used as electrolyte ions that may be involved in electrochromic reactions, for example, coloring or decolorization of the metal oxide layer.
  • the presence of monovalent cations in the layer contributes to the transfer of monovalent cations between the electrolyte and each layer that is required later for the reversible discoloration reaction, and allows the initialization work to be omitted, as described below.
  • the first metal oxide layer there is a cation wherein the monovalent cation is a metal oxide layer
  • cm 2 1.0 ⁇ 10 per - 8 mol to 1.0 ⁇ 10 - content range of 6 mol, more specifically, 5.0 ⁇ 10 - 8 mol to 1.0 ⁇ 10 - 7 mol may be present in a content range.
  • the monovalent cation is present in the above content range, the above-described object can be achieved.
  • the one on the metal oxynitride layer there is a cation wherein the monovalent cations, metal oxynitride layers cm 2 per 5.0 ⁇ 10 - 9 mol to 5.0 ⁇ 10 - content range of 7 mol, more specifically, the 2.5 ⁇ 10 - 7 mol content may be in the range - 8 mol to 2.5 ⁇ 10.
  • the monovalent cation is present in the above content range, the above-described object can be achieved.
  • the content of monovalent cations present in each layer can be determined from the relationship between the charge amount of each layer in which the monovalent cation is present and the number of moles of electrons.
  • the amount of charge of the metal oxynitride layer in the conductive laminate is A (C / cm 2 ). If the charge amount A divided by the Faraday constant F (A / F) is the metal oxynitride layer cm 2 It may be the number of moles of electrons present in the sugar.
  • the maximum content of the monovalent cation present in each layer may be equal to the mole number of the electrons obtained from the above.
  • the method of measuring the amount of charge is not particularly limited, and a known method can be used.
  • the amount of charge can be measured by potential step chrono amperometry (PSCA) using a potentiostat device.
  • the presence of monovalent cations in some layers of the layered composition constituting the conductive laminate is a potentiostat device. It can be made using. Specifically, a three-electrode potentiometer device comprising a counter electrode including an operating electrode, a reference electrode containing Ag, and a lithium foil is provided in an electrolyte solution containing a monovalent cation, and the conductive laminate is connected to the operating electrode. Thereafter, the monovalent cation can be inserted into the conductive laminate by applying a predetermined voltage.
  • the magnitude of the predetermined voltage applied for the monovalent cation insertion may include the degree of content of the monovalent cations included in the electrolyte described below, the degree of insertion of the monovalent cations required in the conductive laminate, the optical properties of the conductive laminate required, Or it may be determined in consideration of the coloring level of the electrochromic layer.
  • the term "coloring level” refers to an electrochemical reaction caused by a voltage of a predetermined magnitude applied to an electrochromic layer or a laminate including the same, and as a result, the electrochromic layer is colored and the layer or As in the case where the transmittance of the laminate is lowered, it may mean the “minimum size (absolute value)” of the voltage applied to the electrochromic layer to cause discoloration (coloring and / or discoloration). For example, when a voltage is applied in the order of -0.1 V, -0.5 V, -1 V and -1.5 V at a predetermined time interval to the conductive laminate, the coloring of the metal oxide layer is prevented from applying -1 V.
  • the coloring level of a metal oxide layer can be said to be 1V. Since the coloring level, i.e., the minimum magnitude (absolute value) of the voltage causing coloring, functions as a kind of barrier for coloring, when a potential of a magnitude smaller than the minimum magnitude (absolute value) of the layer coloring level is applied, In fact, the coloring of the layer does not occur (although a slight discoloration occurs, it is difficult to be seen by the observer).
  • the colored levels of the metal oxynitride layer and the metal oxide layer may be different from each other. More specifically, the metal oxynitride layer may also be colored and bleached by an electrochemical reaction like the metal oxide layer, but the minimum magnitude (absolute value) of the voltage causing the coloring of the metal oxide layer and the metal The minimum magnitudes (absolute values) of the voltages that cause coloring of the oxynitride layers may differ from one another. For this purpose, as described above, the type and / or content of the metal included in each layer oxide and oxynitride may be appropriately adjusted.
  • the colored level of the metal oxynitride layer may have a value greater than the colored level of the metal oxide layer.
  • the coloring level of the metal oxide layer may be 0.5V.
  • the coloring level of the metal oxynitride layer may be 1V.
  • the coloring level of the metal oxynitride layer may be 2V or 3V.
  • the coloring level of the metal oxide layer having the above configuration may be 1V.
  • the metal oxide layer of the conductive laminate can be colored. More specifically, by appropriately adjusting the predetermined voltage applied during the insertion of the monovalent cation described above, the metal oxynitride layer having a higher color level than the metal oxide layer can be colored, and only the metal oxide layer can be colored. have.
  • the light transmittance of the colored metal oxide layer may be 45% or less or 40% or less, and the uncolored metal oxynitride layer may maintain visible light transmittance of 60% or more or 70% or more.
  • the light transmittance of the conductive laminate including the colored metal oxide layer may be 45% or less, 40% or less, 35% or less, or 30% or less.
  • the lower limit of the light transmittance of the conductive laminate including the colored metal oxide layer is not particularly limited, but may be, for example, 20% or more.
  • the oxynitride layer including the oxynitride of Chemical Formula 1 may be colored under a voltage application condition of -2 V or less, for example, -2.5 V or less or -3 V or less. That is, the coloring level of the oxynitride layer may be 2 V, 2.5 V or 3 V. For example, when a voltage of ⁇ 1.5 V and ⁇ 2.0 V is applied to the conductive laminate or a device including the same at predetermined time intervals, the oxynitride layer may gradually become colored after the time when ⁇ 2.0 V is applied. (Coloring may be visible to the user).
  • the oxynitride layer satisfying Formula 1 may be colored in a (dark) gray or black color.
  • the coloring level of an oxynitride layer may change to some extent according to the structure used together with an electrochromic film in the range of 2V or more.
  • the conductive layer may have a thickness of 50 nm to 400 nm or less.
  • the conductive layer may include a transparent conductive compound, a metal mesh, or OMO (oxide / metal / oxide), and may be referred to as an electrode layer.
  • ITO Indium Tin Oxide
  • IGO Indium Galium Oxide
  • FTO Fluor doped Tin Oxide
  • AZO Alignium
  • Zinc Oxide GZO
  • Galium doped Zinc Oxide GZO
  • Antimony doped Tin Oxide ATO
  • Indium doped Zinc Oxide IZO
  • Niobium doped Titanium Oxide NTO
  • Zink Oxide ZnO
  • Cesium Tungsten Oxide (CTO) Etc can be mentioned.
  • the materials listed above are not limited to the material of the transparent conductive compound.
  • the metal mesh used for the conductive layer may include Ag, Cu, Al, Mg, Au, Pt, W, Mo, Ti, Ni, or an alloy thereof, and may have a lattice form.
  • the materials usable for the metal mesh are not limited to the metal materials listed above.
  • the conductive layer may include oxide / metal / oxide (OMO). Since the OMO has a lower sheet resistance than the transparent conductive oxide represented by ITO, it is possible to improve the electrical properties of the conductive laminate, such as reducing the discoloration rate of the electrochromic device.
  • OMO oxide / metal / oxide
  • the OMO may include a top layer, a bottom layer, and a metal layer provided between the two layers.
  • the upper layer may mean a layer located relatively farther from the metal oxynitride layer among the layers constituting the OMO.
  • the top and bottom layers of the OMO electrode may comprise oxides of Sb, Ba, Ga, Ge, Hf, In, La, Se, Si, Ta, Se, Ti, V, Y, Zn, Zr or their alloys. It may include.
  • the type of each metal oxide included in the upper layer and the lower layer may be the same or different.
  • the thickness of the top layer may range from 10 nm to 120 nm or from 20 nm to 100 nm.
  • the visible light refractive index of the upper layer may be in the range of 1.0 to 3.0 or 1.2 to 2.8. When having a refractive index and a thickness in the above range, an appropriate level of optical properties can be imparted to the conductive laminate.
  • the thickness of the lower layer may range from 10 nm to 100 nm or from 20 nm to 80 nm.
  • the visible light refractive index of the lower layer may be in the range of 1.3 to 2.7 or 1.5 to 2.5.
  • the metal layer included in the OMO electrode may include a low resistance metal material.
  • a low resistance metal material for example, one or more 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 having a refractive index and a thickness in the above range, an appropriate level of optical properties can be imparted to the conductive laminate.
  • the present application relates to an electrochromic device.
  • the electrochromic device may sequentially include the above-described conductive laminate, electrolyte layer, and counter electrode layer.
  • One surface of the conductive laminate, the electrolyte layer, and the counter electrode layer may directly contact each other, or a separate layer or other configuration may be interposed therebetween.
  • the electrochromic device may be configured such that the metal oxynitride layer is located closest to the electrolyte layer of the conductive laminate. More specifically, the electrochromic device may sequentially include a conductive layer, a metal oxide layer, a metal oxynitride layer, an electrolyte layer, and a counter electrode layer.
  • the conductive laminate includes an electrochromic metal oxide and a metal oxynitride layer.
  • the metal oxide may include a reducing discoloration material or an oxidizing discoloration material.
  • the metal oxide layer includes a reducing discoloration material, since the two metal components included in the metal oxynitride layer are selected from metals that can be used in the metal oxide layer, the metal oxide layer is included in the conductive laminate.
  • the metal oxynitride layer and the metal oxide layer are considered to have similar physical / chemical properties.
  • the electrolyte ions when electrolyte ions are inserted from the electrolyte layer into the conductive laminate, the electrolyte ions can be inserted into the metal oxide layer, which is an electrochromic layer, without interference by the metal oxynitride layer. The same applies to the case where electrolyte ions are released from each layer.
  • the metal oxynitride layer is determined to improve the driving characteristics of the electrochromic device. Specifically, since there is a difference in reactivity or oxidation tendency between the metal components used in each layer, when the movement of electrolyte ions between layers is repeated, the metal used in any layer, for example, a conductive layer or a metal layer, elutes. There may be a problem. This problem is more clearly observed when OMO is used. However, in the present application, since the metal oxynitride layer capable of containing electrolyte ions functions as a kind of buffer or passivation layer, deterioration of the metal material used for each layer, such as a conductive layer or a metal layer, Can be prevented.
  • the electrochromic device of the present application can have excellent durability, improved discoloration speed, and sufficiently improved usable level.
  • the present application can more precisely control the optical properties of the electrochromic device.
  • the configuration of the counter electrode layer is not particularly limited. For example, it may have the same material and / or the same configuration as the conductive layer described above.
  • the electrolyte layer may be configured to provide electrolyte ions involved in the electrochromic reaction.
  • Electrolyte ions may be monovalent cations, such as H + , Li + , Na + , K + , Rb + , or Cs + , which are inserted into the conductive laminate and may participate in the discoloration reaction.
  • the kind of electrolyte included in the electrolyte layer is not particularly limited.
  • liquid electrolytes, gel polymer electrolytes or inorganic solid electrolytes can be used without limitation.
  • the specific composition of the electrolyte used in the electrolyte layer is not particularly limited as long as it can include a compound capable of providing a monovalent cation, that is, H + , Li + , Na + , K + , Rb + , or Cs + .
  • the electrolyte layer may be LiClO 4 , LiBF 4 , LiAsF 6 , or LiPF 6. It may include a lithium salt compound, such as, or a sodium salt compound such as NaClO 4 .
  • the electrolyte may further include a carbonate compound as a solvent.
  • a carbonate type compound has high dielectric constant, ionic conductivity can be improved.
  • a solvent such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) or ethylmethyl carbonate (EMC) may be used as the carbonate-based compound.
  • the electrolyte layer comprises a gel polymer electrolyte
  • a gel polymer electrolyte for example, polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polymethyl methacrylate (Polymethyl methacrylate, PMMA), polyvinyl chloride (PVC), polyethylene oxide (PEO), polypropylene oxide (PPO), poly (vinylidene fluoride-hexafluoro fluoropropylene) (Poly (vinylidene fluoride-hexafluoro propylene), PVdF-HFP), polyvinyl acetate (Polyvinyl acetate, PVAc), polyoxyethylene (Polyoxyethylene, POE), polyamideimide (Polyamideimide, PAI) and the like polymers may be used.
  • PVdF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PAN polymethyl methacrylate
  • PMMA polymethyl methacrylate
  • the light transmittance of the electrolyte layer may range from 60% to 95%, and the thickness thereof may range from 10 ⁇ m to 200 ⁇ m, but is not particularly limited.
  • the electrochromic device of the present application may further include an ion storage layer.
  • the ion storage layer may refer to a layer formed to balance the charge balance with the metal oxide layer and / or the metal oxynitride layer during the reversible oxidation / reduction reaction for discoloration of the electrochromic material.
  • An ion storage layer may be located between the electrode layer and the electrolyte layer.
  • the ion storage layer may include an electrochromic material having a color development characteristic different from that of the electrochromic material used for the metal oxide layer.
  • the metal oxide layer includes a reducing color change material
  • the ion storage layer may include an oxidative color change material. The reverse is also possible.
  • the ion storage layer may include an oxidative discoloration material. Specifically, oxides of Cr, Mn, Fe, Co, Ni, Rh, or Ir; Hydroxides of Cr, Mn, Fe, Co, Ni, Rh, or Ir; And one or more selected from prussian blue may be included in the ion storage layer.
  • the thickness of the ion storage layer may range from 50 nm to 450 nm, and the light transmittance may range from 60% to 95%.
  • each layer containing the electrochromic materials should have the same colored or discolored state.
  • the metal oxide layer containing the reductive electrochromic material is colored
  • the ion storage layer including the oxidative electrochromic material should also have a colored state.
  • the metal oxide layer containing the reductive electrochromic material is decolorized.
  • the ion storage layer containing the oxidative electrochromic material should also be decolorized.
  • two electrochromic materials having different color development properties do not contain electrolyte ions by themselves, there is additional work to match the coloration or decolorization state between layers containing each electrochromic material. Is required.
  • these tasks are called initialization tasks.
  • the first layer contains transparent WO 3 which is colored by reduction but is almost colorless in itself, and the Prussian blue colored as such is included in the second layer
  • a high voltage is applied to a second layer of an electrochromic device in which an electrode layer, a first layer, an electrolyte layer, a second layer, and an electrode layer are laminated to perform decolorization treatment (reduction treatment) on Prussian blue.
  • decolorization treatment reduction treatment
  • the initialization work performed at a high potential has a problem of lowering the durability of the device, such as causing side reactions between the electrode and the electrolyte layer.
  • a monovalent cation that can be used as an electrolyte ion is previously inserted into a conductive laminate, and in some cases, a metal oxide layer and / or a metal oxynitride layer Since it may be colored, the above initialization operation is not necessary. Therefore, the device can be driven without deterioration in durability due to the initialization operation.
  • the electrochromic device may further include a substrate.
  • the substrate may be located on an outer surface of the device, specifically, an outer surface of the conductive layer of the counter electrode layer or the conductive laminate.
  • the substrate may also be light transmissive, ie having a light transmittance in the range of 60% to 95%. If the transmittance in the above range is satisfied, the kind of substrate to be used is not particularly limited.
  • glass or polymer resins can be used. More specifically, a polyester film such as polycarbonate (PC), polyethylene (phthalene naphthalate) (PEN) or polyethylene (ethylene terephthalate) (PET), an acrylic film such as poly (methyl methacrylate) (PMMA), or polyethylene (PE) Or a polyolefin film such as PP (polypropylene) may be used, but is not limited thereto.
  • the electrochromic device may further include a power source.
  • the manner of electrically connecting the power source to the device is not particularly limited and may be appropriately made by those skilled in the art.
  • the voltage applied by the power source may be a constant voltage.
  • the power source may alternately apply a voltage at a level capable of discoloring and coloring the electrochromic material for a predetermined time interval.
  • the power source may change the magnitude of the voltage applied at predetermined time intervals.
  • the power supply may apply a plurality of coloring voltages that sequentially increase or decrease at predetermined time intervals, and may apply a plurality of decolorization voltages that sequentially increase or decrease at predetermined time intervals. .
  • the power source may sequentially apply the colored level of the metal oxide layer and the colored level of the metal oxynitride layer.
  • the metal oxide layer is first colored, and then the metal oxynitride layer is additionally colored. Accordingly, the electrochromic device of the present application can realize a very low level of light transmittance, for example, a light transmittance of 10% or less or 5% or less in a state of being colored to the metal oxynitride layer.
  • the metal oxide layer and / or the ion storage layer is colored, for example, if the light transmittance of about 20% or 15% can be achieved, in the device of the present application to which the metal oxynitride is gradually colored 10 Visible light transmittance of less than or equal to 5% may be realized.
  • This level of light transmittance is a value that is difficult to realize in the prior art using only the configuration corresponding to the metal oxide layer and the ion storage layer. Further, in the prior art using only the structures corresponding to the metal oxide layer and the ion storage layer, it is not expected to finely adjust the light transmittance step by step as in the present application.
  • an electrochromic conductive laminate is provided.
  • the conductive laminate and the electrochromic device including the same have excellent durability as well as an improved electrochromic speed.
  • FIG. 1 is a graph showing a state in which a laminate including a metal oxynitride layer of the present application having a translucent and electrochromic state is driven without deterioration of durability when a voltage of ⁇ 5 V is applied.
  • Figure 2 is a graph relating to driving characteristics of the device. Specifically, Figure 2 (a) is a graph showing the change in the charge amount of the device of Example 1 as the cycle increases, Figure 2 (b) shows the change in the charge amount of the device of Comparative Example 1 as the cycle increases. It is a graph shown.
  • Figure 3 is a graph relating to driving characteristics of the device. Specifically, Figure 3 (a) is a graph showing the change in the amount of current and charge measured in accordance with Example 2 in a specific cycle period (second time), Figure 3 (b) is measured in accordance with Comparative Example 2 The graph shows the change in the amount of current and charge in a specific cycle period.
  • Figure 4 is a graph showing the optical characteristics of the electrochromic device of the present application that can adjust the transmittance step by step according to the applied voltage.
  • ITO having a light transmittance of about 90% was formed on one surface of glass (galss) having a light transmittance of about 98%.
  • an oxynitride (Mo a Ti b O x N y ) layer including Mo and Ti was formed on a surface of ITO (as opposed to the glass position) by using sputter deposition to a thickness of 30 nm.
  • the weight percent ratio of the target of Mo and Ti was 1: 1, the deposition power was 100 W, the process pressure was deposited at 15 mTorr, and each flow rate of Ar, N 2 and O 2 was 30 sccm, 5 sccm, and 5 sccm.
  • the flow rate of nitrogen was 10 sccm, and the oxynitride layer was formed in the same manner as in Preparation Example 1, except that the content ratio was changed as shown in Table 1.
  • the flow rate of nitrogen was 15 sccm, and the oxynitride layer was formed in the same manner as in Preparation Example 1, except that the content ratio was changed as shown in Table 1.
  • the oxynitride layers of Preparation Examples 2 to 4 have a very low transmittance, but the oxynitride layer comprising the oxynitride of Preparation Example 1 has a transmittance of about 90%.
  • the oxynitride layer of Preparation Example 1 having high light transmittance is suitable as a member for an electrochromic device.
  • the glass / ITO / oxynitride (Mo a Ti b O x N y ) laminate prepared from Preparation Example 1 was immersed in an electrolyte containing LiClO 4 (1M) and propylene carbonate (PC). At 25 ° C., a coloring voltage of ⁇ 3 V and a decolorization voltage of +3 V were applied alternately for 50 seconds, respectively.
  • the currents, transmittances, and discoloration times at the time of coloring and decolorization thus measured are as listed in Table 2.
  • the laminate of Preparation Example 1 has discoloration characteristics (coloring) according to the voltage applied.
  • 1 is a graph which records the state in which the laminated body of manufacture example 1 drives (electrochromic) when a drive electric potential is +/- 5V.
  • Mo a Ti b O x N y having the same content ratio as the oxynitride of Preparation Example 1
  • a conductive laminate comprising a layer, a WO 3 layer, and an OMO electrode layer was sequentially prepared.
  • 100 ppm of an electrolytic solution containing LiClO 4 (1M) and propylene carbonate (PC) and a potentiostat device were prepared, and a voltage of ⁇ 1 V was applied for 50 seconds to provide Mo a Ti b O x N y. Li + in the layer and WO 3 layer Inserted. It was confirmed that the WO 3 layer was colored in a blue series color.
  • the content of Li + present per cm 2 WO 3 layer is 1.0 ⁇ 10 -8 mol to 1.0 ⁇ 10 - 6 mol are included in the range, Mo a Ti b O x N y
  • the content of the Li + layer present per cm 2 was 5.0 ⁇ 10 - it was confirmed is included in the range to 7 mol range - 9 mol to 5.0 ⁇ 10.
  • the manufactured electrochromic device has a laminated structure of OMO / WO 3 / Mo a Ti b O x N y / GPE / PB / ITO.
  • the change in charge amount of the device over time was observed while repeatedly applying a bleaching voltage and a coloring voltage to the manufactured device at regular intervals.
  • the decolorization voltage per cycle was applied for 50 seconds at (+) 1.0 V, and the coloring voltage was applied for 50 seconds selected from the range of (-) 1.0 to (-) 3.0 V.
  • the result is shown in FIG. 2 (a).
  • An electrochromic device was prepared in the same manner except that the Mo a Ti b O x N y layer was not included, and the charge amount change of the device was observed in the same manner. The result is shown in FIG. 2 (b).
  • the level at which cycling can be performed while the device is not damaged when driving the device is called an available level of the device.
  • Mo a Ti b O x N y The embodiment including the layer does not decrease the amount of charge even if more than 1,000 cycling is performed, it can be said that the usable level is improved compared to the comparative example.
  • FIG. 3 (a) shows that the peaks of the charge amount and the current are steep. Specifically, FIG. 3 (b) shows the time required for the charge amount and the current to converge to a specific value in the range of approximately 20 seconds to 30 seconds, while FIG. 3 (a) shows that time within 10 seconds. This means that the discoloration speed in the example device is faster than that of the comparative device.
  • the laminate and the electrochromic device of the present application including two layers having different colored levels from each other can be controlled in stages of light transmittance.
  • the light blocking property is very high.
  • the metal oxide layer including WO 3 is colored in light blue
  • the metal oxynitride layer including Mo and Ti is dark gray. It can be seen that very low light transmittance is observed while coloring with).

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

Abstract

La présente invention concerne un stratifié conducteur et un dispositif électrochromique comprenant ce dernier. Le stratifié conducteur comprend une couche d'oxynitrure métallique, une couche d'oxyde métallique et une couche conductrice. Le stratifié conducteur et le dispositif électrochromique selon la présente invention présentent non seulement une durabilité supérieure et s'avèrent excellents en termes de taux de changement de couleur, mais peuvent également commander des propriétés optiques de façon progressive.
PCT/KR2018/004674 2017-04-24 2018-04-23 Stratifié conducteur et dispositif électrochromique comprenant ce dernier WO2018199572A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US16/604,893 US20200255723A1 (en) 2017-04-24 2018-04-23 Conductive laminate and an electrochromic device comprising the same
EP18790462.8A EP3618082A4 (fr) 2017-04-24 2018-04-23 Stratifié conducteur et dispositif électrochromique comprenant ce dernier
CN201880027087.8A CN110574127A (zh) 2017-04-24 2018-04-23 导电层合体和包括其的电致变色装置
JP2019557571A JP2020518003A (ja) 2017-04-24 2018-04-23 導電性積層体およびそれを含む電気変色素子

Applications Claiming Priority (4)

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KR10-2017-0052043 2017-04-24
KR20170052043 2017-04-24
KR10-2018-0045421 2018-04-19
KR1020180045421A KR20180119120A (ko) 2017-04-24 2018-04-19 도전성 적층체 및 이를 포함하는 전기변색소자

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Citations (5)

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KR20080086655A (ko) * 2007-03-23 2008-09-26 주식회사 엘지화학 내수성이 우수한 전기변색소자용 전극 및 그 제조방법
US20100053722A1 (en) * 2008-08-28 2010-03-04 Ppg Industries Ohio, Inc. Electrochromic device
US20120258295A1 (en) * 2011-04-08 2012-10-11 Saint-Gobain Performance Plastics Corporation Multilayer component for the encapsulation of a sensitive element
KR101221754B1 (ko) * 2010-10-05 2013-01-11 제이 터치 코퍼레이션 전기변색 모듈 및 그 모듈을 구비한 입체영상 표시장치
KR101528015B1 (ko) * 2010-02-19 2015-06-10 쌩-고벵 글래스 프랑스 직렬-접속된 전지를 갖는 전기변색 글레이징 및 그의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080086655A (ko) * 2007-03-23 2008-09-26 주식회사 엘지화학 내수성이 우수한 전기변색소자용 전극 및 그 제조방법
US20100053722A1 (en) * 2008-08-28 2010-03-04 Ppg Industries Ohio, Inc. Electrochromic device
KR101528015B1 (ko) * 2010-02-19 2015-06-10 쌩-고벵 글래스 프랑스 직렬-접속된 전지를 갖는 전기변색 글레이징 및 그의 제조 방법
KR101221754B1 (ko) * 2010-10-05 2013-01-11 제이 터치 코퍼레이션 전기변색 모듈 및 그 모듈을 구비한 입체영상 표시장치
US20120258295A1 (en) * 2011-04-08 2012-10-11 Saint-Gobain Performance Plastics Corporation Multilayer component for the encapsulation of a sensitive element

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