WO2019199012A1 - Film électrochromique - Google Patents

Film électrochromique Download PDF

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Publication number
WO2019199012A1
WO2019199012A1 PCT/KR2019/004185 KR2019004185W WO2019199012A1 WO 2019199012 A1 WO2019199012 A1 WO 2019199012A1 KR 2019004185 W KR2019004185 W KR 2019004185W WO 2019199012 A1 WO2019199012 A1 WO 2019199012A1
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Prior art keywords
layer
electrochromic
protective layer
electrochromic film
oxide
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PCT/KR2019/004185
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English (en)
Korean (ko)
Inventor
김용찬
김기환
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190039882A external-priority patent/KR20190118121A/ko
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Publication of WO2019199012A1 publication Critical patent/WO2019199012A1/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 an electrochromic film.
  • Electrochromic refers to a phenomenon in which the optical properties of an electrochromic active material are changed by an electrochemical oxidation or reduction reaction.
  • the electrochromic active material may change optical properties such as intrinsic color or transmittance, for example, as a result of electron transfer or oxidation / reduction reaction occurring when a voltage is applied from the outside.
  • the electrochromic device using the above phenomenon is largely composed of a working electrode, a counter electrode, and an electrolyte like a battery.
  • the inorganic-based electrochromic material is generally formed in a film or film form on a transparent conductive electrode such as ITO.
  • ions such as Li + are inserted into and / or released from the electrochromic material-containing layer in the electrolyte, and at the same time, electrons moving through an external circuit are also electrochromic.
  • the electron density of the electrochromic material changes as it participates in chemical reactions in the material containing layer, and as a result, the optical properties change as the color of the layer changes.
  • the state in which the light transmittance of the device is lowered is represented as colored
  • the state in which the light transmittance of the device is increased is represented as bleached.
  • the change in the optical properties of the electrochromic device may be repeated through the change in the polarity of the voltage applied to the electrode. Therefore, even when the repetition of coloring and discoloration, that is, the driving cycle of the device increases, the degree of change in the optical properties of the device needs to be maintained without deterioration.
  • One object of the present application is to provide an electrochromic film having excellent driving characteristics, that is, excellent driving durability.
  • Another object of the present application is to provide an electrochromic film that can be clearly transmitted to a user without distorting the optical property change of the electrochromic material.
  • the present application relates to an electrochromic film.
  • the electrochromic film includes an electrolyte layer, an electrochromic layer, and an electrode layer. Specifically, the electrochromic film includes an electrolyte layer, an electrochromic layer, and an electrode layer sequentially.
  • the electrochromic layer is a layer containing an electrochromic material capable of changing its intrinsic color by oxidation or reduction.
  • an acidic or basic environment may be formed inside the electrochromic film.
  • electrochromic materials include Ni, Co, or Mn may collapse. have.
  • the layer comprising the material may also degrade. This may affect the dissolution of the electrode layer, and may cause a problem of peeling of each layer constituting the electrochromic device or the film. As a result, as the driving time increases, there is a problem that the driving durability of the device is drastically lowered.
  • the color change that the discoloration material may have is a property inherent in the material, when the color required by the user is specified or the color used in the specific application is limited in terms of the color implemented by the discoloration film, only durability is achieved. It is difficult to select and use only discoloring materials that are known to have excellent durability.
  • the inventors of the present application have led to the development of an electrochromic film having excellent durability while being able to be clearly transmitted to the user without distorting the optical property change caused by the color change material.
  • the electrochromic film of the present application includes a protective layer having the characteristics described below in a predetermined position.
  • the protective layer used in the electrochromic film of the present application may include a metal oxide. More specifically, the protective layer may include at least one of Si oxide (SiOx) and Al oxide (AlOx).
  • the metal oxide means a case containing substantially only a metal component and an oxygen component, and is used in a meaning distinguished from a metal oxynitride. This is because the oxynitride may not satisfy the permeability (transparency) or extinction coefficient described below.
  • the protective layer may have a single layer form of Si oxide or a single layer form of Al oxide.
  • the protective layer may have a form in which a single layer of Si oxide and a single layer of Al oxide are directly contacted and stacked.
  • the protective layer may have a form including Si oxide and Al oxide in one layer.
  • the oxygen content (atomic%) in the Si oxide (SiOx) or Al oxide (AlOx) included in the protective layer is not particularly limited.
  • the oxide of the protective layer may contain oxygen in a stoichiometrically stable content at a level that satisfies the characteristics described below and at the same time can have adequate adhesion with adjacent layers.
  • the protective layer having the above configuration may be a layer having transparency.
  • the protective layer may be a layer having an extinction coefficient (k) of less than 0.1 measured at a wavelength of visible light in the range of 380 to 780 nm.
  • the extinction coefficient k may be calculated as ⁇ / 4 ⁇ I (dI / dx).
  • the extinction coefficient k is a value obtained by multiplying ⁇ / 4 ⁇ by the reduction ratio dI / I of the light intensity per path unit length dx in the protective layer, for example, 1 m.
  • ⁇ is the wavelength of light.
  • the extinction coefficient range may include both the upper limit of the maximum value of the extinction coefficient value measured in the wavelength band less than 0.1 and the case where the arithmetic mean value of the extinction coefficient value measured in each wavelength band is less than 0.1.
  • the extinction coefficient may also be referred to as an absorption coefficient, and is a factor that defines how strongly the composition absorbs light at a specific wavelength or estimates the transmittance of the protective layer. For example, if the extinction coefficient satisfies the above value, it can be considered transparent. In addition, when the extinction coefficient does not satisfy the above value, for example, exceeds 0.1 or increases to 0.2 or more, the light transmittance may decrease and the light absorbency or reflectivity may become strong. When the reflectivity is increased, the color change of the discoloration material may be distorted, and when the light absorbency is increased, it is difficult to visually recognize the color change of the film. That is, when the protective layer satisfies the extinction coefficient range, the protective layer may have sufficient light transmittance or transparency, and thus the change in the optical properties of the electrochromic layer may be clearly visible to the user without distortion.
  • the protective layer may be a layer having an extinction coefficient K 380 of less than 0.1 measured at a wavelength of 380 nm.
  • the protective layer may be a layer having an extinction coefficient (K 400 ) measured at a wavelength of 400 nm less than 0.1.
  • the protective layer may be a layer having an extinction coefficient K 550 of less than 0.1 measured at a wavelength of 550 nm.
  • the protective layer may be a layer having an extinction coefficient K 780 of less than 0.1 measured at a wavelength of 780 nm.
  • the extinction coefficient value is "0" it means that the extinction coefficient is substantially zero or close to zero.
  • the extinction coefficient of the protective layer is 0.01 or less, 0.001 or less, or 0.0001 or less. Can be.
  • the protective layer When the protective layer satisfies the extinction coefficient and has light transmittance, a small amount of other components may be included in addition to the Si oxide and the Al oxide.
  • the protective layer may further include an oxide such as In, Ti, or Sn, in addition to Al oxide or Si oxide.
  • the term "small amount" means that the content of components other than Al oxide (or Si oxide) is 10 wt% or less, 5 wt% or less, 1 wt% or less, 0.1 wt% or less, or 0.01 based on the total weight of the protective layer. It may mean the case that the weight% or less.
  • the refractive index (n) of the protective layer satisfying the extinction coefficient may be in the range of 1.50 to 2.50.
  • the refractive index may be a refractive index measured at a visible light wavelength in the range of 380 to 780 nm.
  • the refractive index can be calculated or measured using a known apparatus or method. For example, when the angle of light incident on the surface of the protective layer is ⁇ 1 , and the refractive angle of light inside the protective layer is ⁇ 2 , the refractive index value can be confirmed by calculating sin ⁇ 1 / sin ⁇ 2 . At this time, the reference plane (or reference line) for measuring ⁇ 1 and ⁇ 2 is the same.
  • An electrochromic device including a protective layer that satisfies the range refractive index may have excellent visibility.
  • the protective layer may be a layer having a refractive index (n 380 ) measured at 380 nm ranging from 1.50 to 2.50.
  • the protective layer may be a layer having a refractive index (n 400 ) measured at 400 nm in a range of 1.50 to 2.50.
  • the protective layer may be a layer having a refractive index (n 550 ) measured at 550 nm ranging from 1.50 to 2.50.
  • the protective layer may be a layer having a refractive index (n 780 ) measured at 780 nm ranging from 1.50 to 2.50.
  • the refractive index of the protective layer measured in the wavelength range or each wavelength may be 1.55 or more, 1.60 or more, 1.65 or more, 1.70 or more, 1.75 or more, 1.80 or more, 1.85 or more, 1.90 or more, 1.95 or more, or 2.00 or more.
  • the upper limit of the protective layer refractive index is not particularly limited, but may be 2.50 or less, 2.45 or less, 2.40 or less, 2.35 or less, 2.30 or less, 2.25 or less, 2.20 or less, 2.10 or less, or 2.05 or less.
  • the refractive index of the protective layer can be appropriately adjusted within the above range.
  • the thickness of the protective layer may range from 1 to 120 nm.
  • the protective layer is, for example, 5 nm or more, 10 nm or more, 20 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more , 65 nm or more, 70 nm or more, 75 nm or more, 80 nm or more, 85 nm or more, or 90 nm or more. If the thickness is too thin, the durability of the protective layer may be lowered due to defects such as pin holes.
  • the thickness of the protective layer may be, for example, 115 nm or less, 110 nm or less, 105 nm or less, or 100 nm or less.
  • the protective layer may be formed using a known dry or wet method.
  • the protective layer may be formed by a dry method such as deposition.
  • a protective layer may be formed using a wet coating method, for example, by applying a heat treatment after coating the Si oxide (and / or Al oxide) -containing coating composition in the form of particles. Given the uniformity of the layer and the extinction coefficient, it may be desirable to use deposition.
  • the electrochromic film may include a metal oxide-containing first protective layer on one surface opposite to one surface of the electrode layer facing the electrochromic layer.
  • phase or “phase” used in connection with an interlayer stacking position includes not only when a configuration is formed directly above another configuration but also when a third configuration is interposed between these configurations. I mean.
  • the electrochromic film may include an electrolyte layer 130, an electrochromic layer 120, an electrode layer 110, and a first protective layer 210 in sequence (see FIG. 1A).
  • the electrode layer is peeled from the adjacent layer while the insertion / desorption of electrolyte ions is repeated as the driving cycle increases.
  • the first protective layer is used at a predetermined position, the peeling problem of the electrode layer may be compensated for, and the long-term driving durability of the electrochromic film may be improved.
  • the change in the optical properties of the electrochromic film can be clearly seen.
  • adjacent layers may directly contact each other.
  • a third configuration may be interposed between adjacent layers. In order to secure interlayer adhesion and durability, adjacent layers may be preferably in direct contact with each other.
  • the electrolyte layer 130 is configured to provide electrolyte ions involved in the electrochromic reaction.
  • the electrolyte ion may be, for example, a monovalent cation such as H + , Li + , Na + , K + , Rb + , or Cs + .
  • electrolyte in the present application is not particularly limited.
  • liquid electrolytes, gel polymer electrolytes or inorganic solid electrolytes can be used without limitation.
  • the electrolyte may be used in the form of one layer or film to be laminated together with the electrode layer or the light transmitting film.
  • the type of electrolyte salt 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 is LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCl, LiBr, LiI, LiB 10 Cl 10 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , Lithium salt compounds such as CH 3 SO 3 Li, CF 3 SO 3 Li, or (CF 3 SO 2 ) 2 NLi; Or sodium salt compounds such as NaClO 4 .
  • the electrolyte layer may comprise a Cl or F element containing compound as the electrolyte salt.
  • the electrolyte layer is LiClO 4 , LiBF 4 , LiAsF 6 , LiPF 6 , LiCl, LiB 10 Cl 10 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CF 3 SO 3 Li And (CF 3 SO 2 ) 2 NLi and NaClO 4 .
  • Such electrolyte salts can create harsh conditions (eg acid conditions) in the device during operation.
  • a protective layer having a predetermined configuration is used, deterioration of the electrochromic material generated under acidic conditions can be suppressed.
  • the electrolyte may further include a carbonate compound as a solvent. Since 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 when the electrolyte layer comprises a gel polymer electrolyte, the electrolyte layer may be poly-vinyl sulfonic acid, poly-styrene sulfonic acid, poly-ethylene sulfonic acid (Poly-ethylene sulfonic acid), poly-2-acrylamido-2methyl-propane sulfonic acid, poly-perfluoro sulfonic acid, poly -Toluene sulfonic acid, poly-vinyl alcohol, poly-ethylene imine, poly-vinyl pyrrolidone, poly-ethylene oxide ( Poly-ethylene oxide (PEO)), poly-propylene oxide (PPO), poly- (ethylene oxide, siloxane) (PEOS), poly- (ethylene glycol, Siloxane) (poly- (ethylene glycol, siloxane)), poly- (propylene oxide, siloxane) (poly- (propylene oxide, siloxane), poly- (ethylene oxide, methyl
  • the thickness of the electrolyte layer may range from 10 ⁇ m to 200 ⁇ m.
  • the electrolyte layer may have a transmittance in the range of 60 to 95%.
  • the electrolyte layer may have a transmittance of 60 to 95% of visible light having a wavelength range of 380 nm to 780 nm, more specifically, 400 nm wavelength or 550 nm wavelength.
  • the transmittance can be measured using a known haze meter (HM).
  • the type of electrochromic material included in the electrochromic layer 120 is not particularly limited.
  • the electrochromic layer may include a reducing discoloration material in which coloring occurs during the reduction reaction.
  • the kind of reducing discoloration material used for the electrochromic layer is not particularly limited.
  • oxides of one or more of Ti, Nb, Mo, Ta, and W may be used as the discoloration material, such as WO 3 , MoO 3 , Nb 2 O 5 , Ta 2 O 5, TiO 2, and the like.
  • the electrochromic layer may include a material that is different in color development properties from the reducing inorganic color change material. That is, an oxidative discoloration material that is colored when oxidized may be included in the electrochromic layer.
  • the kind of oxidative discoloration material used for the electrochromic layer is not particularly limited.
  • the oxidative discoloration material is selected from Cr, Mn, Fe, Co, Ni, Rh, and Ir, such as LiNiOx, IrO 2 , NiO, V 2 O 5 , LixCoO 2 , Rh 2 O 3, or CrO 3, and the like. It may be one or more oxides.
  • one or more hydroxides selected from Cr, Mn, Fe, Co, Ni, Rh, and Ir may be used as the oxidative discoloration material of the electrochromic layer.
  • prussian blue may be used as the oxidative discoloration material of the electrochromic layer.
  • the electrochromic layer may have a thickness in the range of 50 nm to 450 nm. Specifically, the thickness of the electrochromic layer may be 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, or 350 nm or more. If the thickness is satisfied, it may contain a sufficient amount of electrolyte ions that can be used for electrochromic.
  • the method of forming the electrochromic layer including the reducing or oxidative discoloring material is not particularly limited.
  • the electrochromic layer can be formed by a dry method such as deposition.
  • the electrochromic layer may be formed by using a wet coating method, for example, by applying an electrochromic material-containing coating composition in the form of particles and then performing heat treatment. Given the uniformity of the layer, it may be desirable to use deposition.
  • the material and the shape of an electrode layer which the electrode layer 110 contains are not specifically limited.
  • the electrode layer may include a transparent conductive compound.
  • the kind of the transparent conductive compound is not particularly limited, but for example, indium tin oxide (ITO), indium oxide (In 2 O 3 ), indium galium oxide (IGO), fluor doped tin oxide (FTO), and aluminum (AZO) doped Zinc Oxide (GZO), Galium doped Zinc Oxide (GZO), Antimony doped Tin Oxide (ATO), Indium doped Zinc Oxide (IZO), Niobium doped Titanium Oxide (NTO), Zinc Oxide (ZnO), or Cesium Tungsten Oxide (CTO) Or the like can be used as the electrode layer forming material.
  • the electrode layer may include a metal.
  • the electrode layer may have a metal mesh shape.
  • the electrode layer may include Ag, Cu, Al, Mg, Au, Pt, W, Mo, Ti, Ni, or an alloy thereof, and may have a lattice form.
  • it is not limited to the metal materials listed above.
  • the electrode layer may have a thickness in the range of 20 nm to 400 nm. Specifically, the electrode layer may have a thickness of, for example, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, or 60 nm or more. In addition, the electrode layer may have a thickness of, for example, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less.
  • the electrode layer may have a transmittance in the range of 60 to 95%.
  • the electrode layer may have a transmittance of 60 to 95% of visible light having a wavelength in a range of 380 nm to 780 nm, more specifically, 400 nm or 550 nm.
  • the transmittance can be measured using a known haze meter (HM).
  • the electrochromic film may further include a base layer.
  • the electrochromic film may include an electrolyte layer 130, an electrochromic layer 120, an electrode layer 110, a first protective layer 210, and a base layer 140 in sequence (FIG. 1B). Reference).
  • adjacent layers may directly contact each other.
  • a third configuration may be interposed between adjacent layers.
  • adjacent layers may be preferably in direct contact with each other.
  • the base layer 110 serves as a support for the electrochromic film.
  • the substrate layer may include a material capable of providing a predetermined rigidity, for example, glass or a polymer resin.
  • the substrate layer may include a polymer resin.
  • polymer resins Compared to the use of glass, polymer resins have the advantage of providing both rigidity and flexibility at the same time.
  • a polyester film such as polycarbonate (PC), poly (ethylene naphthalate) or PEN (polyester ethylene terephthalate), an acrylic film such as PMMA (poly (methyl methacrylate)), or PE (polyethylene) or A polyolefin film such as PP (polypropylene) may be used as the base layer material, but is not limited thereto.
  • the substrate layer may have a thickness in the range of 30 nm to 500 ⁇ m.
  • the thickness of the base layer is, for example, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, or 1 ⁇ m or more.
  • the upper limit of the thickness of the substrate layer may be, for example, 400 ⁇ m or less, 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 10 ⁇ m or less, or 5 ⁇ m or less.
  • the base layer may have a transmittance in the range of 60 to 95%.
  • the base layer may have a transmittance of 60 to 95% of visible light having a wavelength in a range of 380 nm to 780 nm, more specifically, 400 nm or 550 nm.
  • the transmittance can be measured using a known haze meter (HM).
  • the electrochromic film may further include an ion storage layer and a counter electrode layer sequentially on one side of the electrolyte layer facing one surface of the electrochromic layer.
  • the electrochromic film includes a counter electrode layer 160, an ion storage layer 150, an electrolyte layer 130, an electrochromic layer 120, an electrode layer 110, and a first protective layer 210. It may be included as (see Figure 1c).
  • the electrochromic film may include a counter electrode layer 160, an ion storage layer 150, an electrolyte layer 130, an electrochromic layer 120, an electrode layer 110, a first protective layer 210, and a base layer ( 140 may be sequentially included (see FIG. 1D).
  • adjacent layers may directly contact each other.
  • a third configuration may be interposed between adjacent layers.
  • adjacent layers may be preferably in direct contact with each other.
  • the ion storage layer 150 is a layer formed to balance the charge balance with the electrochromic layer during the reversible oxidation / reduction reaction for discoloration of the electrochromic material.
  • the ion storage layer may include an electrochromic material different in color development properties from the electrochromic material used in the electrochromic layer.
  • the electrochromic layer may include a reducing color change material
  • the ion storage layer may include an oxidative color change material. And vice versa.
  • the ion storage layer and the electrochromic layer use materials having different color development characteristics, that is, mutually complementary color change (reaction) materials, it may be advantageous to balance charge.
  • the ion storage layer may include a color change material derived from Ni, Co, and / or Mn. Since the electrochromic film of the present application includes the protective layer, even when an oxide or hydroxide of Ni, Co, and / or Mn, which is known to be poor in long term driving durability under acidic conditions, is used as a discoloring material, It can provide excellent visibility.
  • the ion storage layer may include one or more oxides selected from Ni, Co, and Mn as the oxidative discoloration material.
  • the ion storage layer may include one or more hydroxides selected from Ni, Co, and Mn as the oxidative discoloring material.
  • the ion storage layer may include at least one oxide selected from Ni, Co, and Mn; And one or more hydroxides selected from Ni, Co, and Mn.
  • the thickness of the ion storage layer may range from 50 to 500 nm.
  • the ion storage layer is 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm At least 170 nm, at least 180 nm, at least 190 nm, or at least 200 nm. If the thickness is satisfied, it may be advantageous to contain a sufficient amount of electrolyte ions that can be used for the electrochromic reaction and to balance the charge with the electrochromic layer.
  • the upper limit of the thickness of the ion storage layer may be, for example, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, or 250 nm or less.
  • the characteristics and the configuration of the counter electrode layer 160 may be the same as those of the electrode layer 110 described above.
  • the electrochromic film may further include a second protective layer.
  • the electrochromic film may include a metal oxide-containing second protective layer on one surface of the counter electrode layer facing one surface of the ion storage layer.
  • the electrochromic film may have a stacking order of the ion storage layer 150, the counter electrode layer 160, and the second protective layer 220.
  • adjacent layers may directly contact each other.
  • a third configuration may be interposed between adjacent layers.
  • adjacent layers may be preferably in direct contact with each other.
  • the configuration or characteristics associated with the second protective layer may be the same as that of the above-described protective layer (eg, the first protective layer).
  • the first protective layer and the second protective layer may include the same or different oxides.
  • the first protective layer and the second protective layer may include an oxide of Si.
  • the first protective layer and the second protective layer may include an oxide of Al.
  • the first protective layer may include an oxide of Si
  • the second protective layer may include an oxide of Al
  • the first protective layer may include an oxide of Al
  • the second protective layer may include an oxide of Si.
  • the first protective layer may include both an Si oxide layer and an Al oxide layer
  • the second protective layer may include an Si oxide layer or an Al oxide layer.
  • the first protective layer may include a Si oxide layer or an Al oxide layer
  • the second protective layer may include both a Si oxide layer and an Al oxide layer.
  • the first protective layer and the second protective layer may each include both an Si oxide layer and an Al oxide layer.
  • the electrochromic film may further include a counter substrate layer.
  • the electrochromic film may have a stacking order of the ion storage layer 150, the counter electrode layer 160, the second protective layer 220, and the counter substrate layer 170.
  • the electrochromic film may include a counter substrate layer 170, a second protective layer 220, a counter electrode layer 160, an ion storage layer 150, an electrolyte layer 130, an electrochromic layer 120,
  • the electrode layer 110 and the first protective layer 210 may be sequentially included (see FIG. 1G).
  • the electrochromic film may include a counter substrate layer 170, a second protective layer 220, a counter electrode layer 160, an ion storage layer 150, an electrolyte layer 130, an electrochromic layer 120, and an electrode layer ( 110, the first protective layer 210, and the base layer 140 may be sequentially included (see FIG. 1H).
  • adjacent layers may directly contact each other.
  • a third configuration may be interposed between adjacent layers.
  • adjacent layers may be preferably in direct contact with each other.
  • the configuration or characteristics associated with the counterpart base layer 170 may be the same as that of the base layer 140 described above.
  • the electrochromic film may further include a power source.
  • the method of electrically connecting the power source to the electrochromic film is not particularly limited and may be appropriately made by those skilled in the art.
  • the power source may apply a voltage of 2.0 V or less, or 1.5 V or less to the film. That is, when driving the electrochromic film having the above configuration, a voltage in the range of -2.0 to +2.0 V or a voltage in the range of -1.5 to +1.5 V may be applied.
  • the electrochromic film may alternately have a colored and a discolored state.
  • the coloring voltage applied to the electrochromic layer may be negative polarity, and conversely, the color fading voltage may be positive polarity.
  • the voltage which brings about coloring of a film can be called coloring voltage
  • the voltage which brings about decolorization of a film can be called decoloring voltage.
  • the voltage applied by the power source may be a constant voltage.
  • the voltage may alternately apply voltages of -2.0 V and +2.0 V, or voltages of -1.5 V and +1.5 V to the electrochromic film.
  • the time for which the decolorization voltage is applied and the time for applying the coloring voltage may be 60 seconds (s) or less, respectively.
  • the time for which each voltage is applied may be 60 seconds, 50 seconds, 40 seconds or 30 seconds.
  • one cycle of discoloration and one coloration process according to the polarity change of the applied voltage is 1 cycle.
  • the period of the cycle may be 120 seconds, which is the sum of 60 seconds of applying the coloring voltage and 60 seconds of applying the discoloring voltage.
  • the transmittance can be measured using known apparatus and methods. For example, known devices such as Solidspec 3700 or ellipsometers can be used to measure the transmittance of electrochromic films.
  • the electrochromic film has a driving capacity or cycle capacity of 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, or 95% or more, calculated by the following formula: It may be a film satisfying the.
  • ⁇ T 1'st is the difference in transmittance between the color transmittance and the decolorization transmittance of the electrochromic film during the first cycle driving
  • ⁇ T 1000'th means the difference in transmittance between the color transmittance and the decolorization transmission during the thousandth cycle driving.
  • the voltage applied during driving is 1.5 V or less, and each time the coloring voltage and the decolorization voltage forming one cycle may be 60 seconds or less.
  • the protective film of the present application including the protective layer can suppress deterioration due to decomposition or dissolution of the layer constituting the electrochromic film, a reduction ratio of ⁇ T 1000'th to ⁇ T 1'st This can satisfy 30% or less. That is, according to the present application, an electrochromic film having excellent long term driving durability is provided.
  • the present application relates to a method of manufacturing an electrochromic film.
  • the method may include sequentially forming an electrode layer and an electrochromic layer on one surface of the first protective layer or the first protective layer-containing laminate.
  • the first protective layer includes at least one of Si oxide and Al oxide, and other materials included in each of the electrode layer and the electrochromic layer are the same as those described above with respect to the electrochromic film.
  • the first protective layer-containing laminate may be a laminate including a first protective layer and a base layer.
  • the base material layer contained in the said laminated body may be a release base material, and the structure which forms the outermost layer of an electrochromic element may be sufficient.
  • the method of forming the first protective layer can be deposition.
  • the first protective layer may be formed by sputter deposition.
  • the conditions for forming a stable thin film are not particularly limited, but for example, the sputtering deposition for forming the protective layer may be performed under a process pressure within a range of 5 to 40 mTorr and a power condition within a range of 50 to 350 W. It may be made while flowing oxygen (O2) at a predetermined flow rate.
  • O2 oxygen
  • sputtering deposition for forming the first protective layer may be performed while adjusting the flow rate of the gas to a predetermined range.
  • the sputtering deposition may be performed by flowing oxygen (O 2) in a vacuum state and generating an argon (Ar) plasma to a metal target (Si or Al) to form a protective layer on the base layer.
  • the flow rate of oxygen, argon or the ratio between them can be adjusted.
  • the sputtering deposition for forming the first protective layer may be performed under the condition that the flow rate of oxygen (O 2) is 5.0 sccm or more.
  • the value of the extinction coefficient may exceed 0.1.
  • the protective layer is less likely to have an extinction coefficient value of less than 0.1 at a wavelength in the range of 380 to 780 nm, specifically at a wavelength of 400 nm or 550 nm.
  • the flow rate of oxygen (O2) injected into the space where the sputtering process is performed is at least 5.5 sccm, at least 6.0 sccm, at least 6.5 sccm, at least 7.0 sccm, at least 7.5 sccm, at least 8.0 sccm, at least 8.5 sccm, at least 9.0 sccm, Or at least 9.5 sccm or at least 10.0 sccm.
  • the upper limit of the flow rate is not particularly limited, but may be, for example, 20 sccm or less or 15 sccm or less.
  • the ratio of the injection flow rate of oxygen (O 2 ) and argon (Ar) during the sputtering deposition for forming the first protective layer may be adjusted. Specifically, assuming that the flow rates of argon (Ar) and oxygen (O 2 ) injected into the space where the sputtering process is performed are flow rates of A sccm and B sccm, these flow rate ratios A (Ar) / B (O 2 ) are And may be maintained in the range of 1.5 to 7.
  • the flow rate ratio A (Ar) / B (O 2 ) may be 1.6 or more, 1.7 or more or 1.8 or more, the upper limit is, for example, 6.5 or less, 6.4 or less, 6.3 or less, 6.2 or less, 6.1 or less, 6.0 or less, 5.9 or less, 5.8 or less, or 5.7 or less.
  • the method of forming the electrode layer is not particularly limited.
  • an electrode layer may be formed on the first protective layer by a deposition method.
  • the electrode layer may be formed on the base layer through thermocompression bonding to a metal film or a metal mesh electrode manufactured separately.
  • the electrode layer may be formed through a predetermined etching (etching) after the metal thin film is formed.
  • the electrochromic layer may be formed by deposition.
  • deposition For example, sputter deposition can be used.
  • the deposition conditions are not particularly limited and may be made while controlling the process conditions according to the type of electrochromic material used.
  • the method may include forming an electrolyte layer on one surface opposite to one surface of the electrochromic layer facing the electrode layer.
  • the electrolyte layer formed to have the above-described configuration can be formed on one surface of the electrochromic layer using a known lamination barrier or the like.
  • the laminate formed by the above-described method (eg, the first protective layer / electrode layer / electrochromic layer or the base layer / first protective layer / electrode layer / electrochromic layer) may be referred to as an upper laminate.
  • the method may further comprise manufacturing a lower laminate.
  • the lower stack may have a stack structure of a counter electrode layer / ion storage layer.
  • the lower laminate may have, for example, a laminated structure of a second protective layer / relative electrode layer / ion storage layer or a laminated structure of a counter substrate layer / second protective layer / relative electrode layer / ion storage layer.
  • the method may include forming an ion storage layer on the counter electrode layer.
  • the method may include sequentially forming a counter electrode layer and an ion storage layer on the second passivation layer.
  • the method may include sequentially forming a second protective layer, a counter electrode layer, and an ion storage layer on the counter substrate layer.
  • the method of forming the second protective layer included in the lower laminate may be the same as that of the first protective layer described above.
  • the material included in each of the counter electrode layer, the ion storage layer, and the counter substrate layer, and a method of forming them may also be the same as described above.
  • the method may further include bonding the upper stack and the lower stack through the electrolyte layer.
  • the bonding method may be made through, for example, known lamination and the like, and is not particularly limited.
  • the material included in the electrolyte layer is the same as described above with respect to the electrochromic film.
  • an electrochromic film excellent in driving durability can be provided.
  • FIG. 1 schematically illustrates the structure of an electrochromic film including a protective layer according to an example of the present application.
  • FIG. 2 is a graph showing the extinction coefficient k and the refractive index n of the protective layers of Preparation Examples 1 to 3.
  • FIG. The extinction coefficient k showing all zero values (consistent with the horizontal axis of the graph) in all three preparation examples is not shown in FIG. 2.
  • the drawn curves relate to Preparation Example 3 (93.8 nm thickness), Preparation Example 2 (62.4 nm thickness), and Preparation Example 1 (36.0 nm thickness) in order from the top.
  • each curve relates to Example 3, Example 1, Example 2, and Comparative Example 1 in order from the top of the graph.
  • a silicon oxide layer (SiOx layer) about 36 nm thick was formed. Specifically, the silicon oxide layer was formed through sputter deposition while flowing oxygen at a process pressure of about 20 mTorr and about 200 W power. At this time, the flow rate of oxygen was maintained at about 5.5 sccm, and the injection flow rate ratio (Ar / O 2 ) of oxygen and argon was maintained at about 6.
  • deposition time was increased to form silicon oxide layers of about 62.4 nm and about 93.8 nm thickness on two different silicon wafers.
  • a silicon oxide layer having a thickness of about 50 nm was prepared in the same manner, except that the flow rate of oxygen was adjusted to 3 sccm and the flow rate ratio of oxygen and argon (Ar / O 2 ) was about 11 when forming the silicon oxide layer. Formed.
  • Preparation of the upper laminate (WO3 / ITO / SiOx / PET) : On one surface of a PET substrate, a silicon oxide layer (SiOx, thickness of about 10 nm), an ITO layer (thickness: about 50 nm), and tungsten oxide (WO3, thickness) About 360 nm) layers were formed sequentially.
  • the silicon oxide layer was formed under the same conditions as the process of Preparation Example 1, except that the PET base layer was used.
  • Preparation of the lower laminate NiOx / ITO / SiOx / PET : on the other of the PET substrate surface, a silicon oxide layer (SiOx, about 10 nm thick), ITO layer (thickness: about 50 nm), and nickel oxide ( NiOx, about 200 nm thick) layers were formed sequentially.
  • the silicon oxide layer was formed under the same conditions as the process of Preparation Example 1, except that the PET base layer was used.
  • electrochromic film An electrochromic film (PET / SiOx / ITO / WO 3 / electrolyte layer / NiOx / ITO / SiOx / PET) was prepared by bonding an upper laminate and a lower laminate through an electrolyte layer. At this time, an electrolyte layer containing propylene carbonate (PC) and LiClO 4 (1M) was used.
  • PC propylene carbonate
  • LiClO 4 (1M) LiClO 4
  • an electrochromic film was prepared in the same manner as in Example 1, except that the protective layer material, the stacking order, and the presence or absence of the protective layer were different.
  • the thickness of the aluminum oxide (AlOx) layer was about 15 nm.
  • the transmittance was specified while alternately applying voltages of -1.5 V and +1.5 V at 60 second intervals, respectively.
  • each cycle is stabilized by driving about 10 cycles from the initial voltage application, and the change in the coloration and decolorization transmittance difference according to the increase in the number of cycles from subsequent cycles was measured (see FIG. 3).
  • Table 2 the difference in coloration and decolorization transmittance ( ⁇ T 1'st ) of the first cycle after stabilization and the difference in coloration and decolorization transmittance ( ⁇ T 1000'th ) of the thousandth cycle was recorded.
  • the transmittance was measured using a haze meter (solidspec 3700).

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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 film électrochromique. Un film électrochromique ayant une configuration prédéterminée selon un mode de réalisation de la présente invention possède une excellente durabilité de pilotage à long terme et procure une excellente visibilité des modifications des propriétés optiques du film.
PCT/KR2019/004185 2018-04-09 2019-04-09 Film électrochromique Ceased WO2019199012A1 (fr)

Applications Claiming Priority (4)

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KR10-2018-0041086 2018-04-09
KR20180041086 2018-04-09
KR10-2019-0039882 2019-04-05
KR1020190039882A KR20190118121A (ko) 2018-04-09 2019-04-05 전기변색필름

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100267992B1 (ko) * 1997-04-11 2000-10-16 구자홍 일렉트로크로믹소자및그제조방법
KR20080040439A (ko) * 2006-11-03 2008-05-08 주식회사 엘지화학 에너지 절약형 스마트 윈도우 및 그 제조 방법
KR20090007687A (ko) * 2006-03-09 2009-01-20 이 잉크 코포레이션 에지 시일을 구비한 전기 광학 디스플레이
KR20150022232A (ko) * 2013-08-22 2015-03-04 엘지디스플레이 주식회사 플렉서블 투명 디스플레이 및 그 제조방법
KR20170115864A (ko) * 2016-04-08 2017-10-18 엘지전자 주식회사 전기변색 소자

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100267992B1 (ko) * 1997-04-11 2000-10-16 구자홍 일렉트로크로믹소자및그제조방법
KR20090007687A (ko) * 2006-03-09 2009-01-20 이 잉크 코포레이션 에지 시일을 구비한 전기 광학 디스플레이
KR20080040439A (ko) * 2006-11-03 2008-05-08 주식회사 엘지화학 에너지 절약형 스마트 윈도우 및 그 제조 방법
KR20150022232A (ko) * 2013-08-22 2015-03-04 엘지디스플레이 주식회사 플렉서블 투명 디스플레이 및 그 제조방법
KR20170115864A (ko) * 2016-04-08 2017-10-18 엘지전자 주식회사 전기변색 소자

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