WO2018199572A1 - Conductive laminate and electrochromic device comprising same - Google Patents

Abstract

The present application relates to a conductive laminate and an electrochromic device comprising the same. The conductive laminate comprises a metal oxynitride layer, a metal oxide layer, and a conductive layer. The conductive laminate and the electrochromic device according to the present application not only have superior durability and are excellent in the rate of color change, but can also gradationally control optical properties.

Description

Conductive laminates and electrochromic devices comprising the same

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0052043 dated April 24, 2017 and Korean Patent Application No. 10-2018-0045421 dated April 19, 2018, and the Korean patent All content disclosed in the literature of the application is included as part of this specification.

Field of technology

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. For example, the working electrode or the counter electrode may include a transparent conductive material and an electrochromic material, respectively, in the form of a film. When a potential is applied to the device, electrolyte ions are inserted into or detached from the electrochromic material-containing film, At the same time, as electrons move through the external circuit, the optical properties of the electrochromic material appear.

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. However, since the insertion and / or desorption of electrolyte ions for changing the optical properties of the entire discoloration layer takes a long time, 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.

On the other hand, in recent years, as the demand for electrochromic devices increases and the field of application is diversified, there is a demand for the development of devices having excellent durability and fine control of optical characteristics.

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 above and other objects of the present application can all be solved by the present application described in detail below.

In one example of the present application, the present application relates to a conductive laminate. The conductive laminate has a variable transmittance characteristic by electrochromic color. Specifically, 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. For example, 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. In this case, 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.

In one example, the metal oxide layer, the metal oxynitride layer, and the conductive layer may have light transmittance. In the present application, 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. When satisfying the light transmittance in the above range, 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. Unless otherwise specified, 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.

In one example, the metal oxide layer may include 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. For example, WO ₃ , MoO ₃ , Nb ₂ O ₅ , Ta ₂ O _5, TiO ₂ , or the like can be used.

In another example, 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. For example, LiNiOx, IrO ₂ , NiO, V ₂ O ₅ , LixCoO _2, Rh ₂ O _3, CrO _3, or the like may be used.

Although not particularly limited, 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. For example, 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.

In one example, the metal oxynitride layer may have an oxynitride including two or more metals selected from Ti, Nb, Mo, Ta and W simultaneously.

More specifically, the metal oxynitride layer may include Mo and Ti at the same time. In this regard, 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. In particular, 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.

 In one example, the metal oxynitride included in the metal oxynitride layer may be represented by the following formula (1).

[Formula 1]

Mo _a Ti _b O _x N _y

In 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, a> 0, b> 0, x> 0, y> 0, 0.5 <a / b <4.0, and 0.005 <y / x <0.02. 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. When the element content ratio (y / x) is satisfied, the metal oxynitride layer may have a light transmittance of 60% or more. In particular, when 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.

In one example, the thin film density (ρ) of the metal oxynitride layer may be 15 g / cm ³ or less. For example, the lower limit of the thin film density (ρ) value may be 0.5 g / cm ³ or more, 0.7 g / cm ³ or more, or 1 g / cm ³ or more, and the upper limit of the thin film density (ρ) 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).

In one example, the thickness of the metal oxynitride layer may be 150 nm or less. For example, 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. When the upper limit of the thickness is exceeded, the insertion or desorption of electrolyte ions may be lowered and may adversely affect the discoloration rate. 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.

In one example, 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. When the metal oxynitride layer has a visible light refractive index in the above range, appropriate light transmittance may be implemented in the conductive laminate.

The method for forming the metal oxynitride layer is not particularly limited. For example, the layer may be formed using various kinds of known deposition methods.

In the present application, monovalent cations may be present in at least one or more layers of the layer structures constituting the conductive laminate. For example, 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. In the present application, 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. In the present application, 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. Although not particularly limited, 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. Thus, 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.

When in one example, 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. When the monovalent cation is present in the above content range, the above-described object can be achieved.

In the case that in one example, 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. When the monovalent cation is present in the above content range, the above-described object can be achieved.

In the present application, the content of monovalent cations present in each layer, that is, the number of moles, 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. For example, when a monovalent cation is inserted into the conductive laminate of the above constitution using a potentiostat device described below, 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. On the other hand, since the electron (e ⁻ ) and the monovalent cation can react with 1: 1, the maximum content of the monovalent cation present in each layer, that is, the maximum mole number, may be equal to the mole number of the electrons obtained from the above. Regarding the content of the monovalent cation, the method of measuring the amount of charge is not particularly limited, and a known method can be used. For example, the amount of charge can be measured by potential step chrono amperometry (PSCA) using a potentiostat device.

In one example, the presence of monovalent cations in some layers of the layered composition constituting the conductive laminate, ie, the insertion of monovalent cations in some layers of 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.

In the present application, 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. If made, 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).

In one example, 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.

In one example, the colored level of the metal oxynitride layer may have a value greater than the colored level of the metal oxide layer. For example, when the coloring level of the metal oxide layer is 0.5V, the coloring level of the metal oxynitride layer may be 1V. Alternatively, when the coloring level of the metal oxide layer is 1V, the coloring level of the metal oxynitride layer may be 2V or 3V. In one example, the coloring level of the metal oxide layer having the above configuration may be 1V.

In one example, only 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. For example, 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. In this case, 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.

In one example, 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.

Although not particularly limited, 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.

In one example, as the transparent conductive compound used in the conductive layer, ITO (Indium Tin Oxide), In ₂ O ₃ (Indium Oxide), IGO (Indium Galium Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium) doped 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), or Cesium Tungsten Oxide (CTO) Etc. can be mentioned. However, the materials listed above are not limited to the material of the transparent conductive compound.

In one example, 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. However, the materials usable for the metal mesh are not limited to the metal materials listed above.

In one example, 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.

The OMO may include a top layer, a bottom layer, and a metal layer provided between the two layers. In the present application, the upper layer may mean a layer located relatively farther from the metal oxynitride layer among the layers constituting the OMO.

In one example, 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.

In one example, the thickness of the top layer may range from 10 nm to 120 nm or from 20 nm to 100 nm. In addition, 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.

In one example, the thickness of the lower layer may range from 10 nm to 100 nm or from 20 nm to 80 nm. In addition, 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. 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.

In one example, the metal layer included in the OMO electrode may include a low resistance metal material. Although not particularly limited, for example, one or more of Ag, Cu, Zn, Au, Pd, and alloys thereof may be included in the metal layer.

In one example, the metal layer may have a thickness in the range of 3 nm to 30 nm or in the range of 5 nm to 20 nm. In addition, the metal layer may have a visible light refractive index of 1 or less or 0.5 or less. When having a refractive index and a thickness in the above range, an appropriate level of optical properties can be imparted to the conductive laminate.

In another example of the present application, 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.

In one example, 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.

As in one example of the present application described above, 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. In one example, when 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. Accordingly, 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.

In addition, 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. As a result, the electrochromic device of the present application can have excellent durability, improved discoloration speed, and sufficiently improved usable level. In addition, as described below, due to the metal oxynitride layer having a different color level from the metal oxide layer, 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. For example, 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 ⁺ . For example, 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 .

In another example, 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. As a non-limiting example, 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.

In another example, when the electrolyte layer comprises 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.

The light transmittance of the electrolyte layer may range from 60% to 95%, and the thickness thereof may range from 10 μm to 200 μm, but is not particularly limited.

In one example, 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. For example, when 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.

In one example, 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.

Although not particularly limited, 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%.

When the electrochromic device includes two electrochromic materials having different color development properties in separate layers, each layer containing the electrochromic materials should have the same colored or discolored state. For example, when 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. On the contrary, the metal oxide layer containing the reductive electrochromic material is decolorized. In this case, the ion storage layer containing the oxidative electrochromic material should also be decolorized. However, as described above, since 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. In general, these tasks are called initialization tasks. For example, if 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, Conventionally, 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. However, 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. On the other hand, in the present application, before lamination of each layer configuration for element formation, 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.

In one example, 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. For example 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.

In one example, the power source may alternately apply a voltage at a level capable of discoloring and coloring the electrochromic material for a predetermined time interval.

In another example, the power source may change the magnitude of the voltage applied at predetermined time intervals. Specifically, 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. .

In another example, when the colored level of the metal oxynitride layer is larger than the colored level of the metal oxide layer, the power source may sequentially apply the colored level of the metal oxide layer and the colored level of the metal oxynitride layer. In this case, 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. That is, when only 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. In addition, in the present application, even if a voltage higher than the coloring level of the metal oxide layer is applied to control the fine light transmittance as described above, deterioration of the metal oxide layer can be prevented because the metal oxynitride layer functions as a kind of passivation layer. .

According to one example of 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. In addition, when using the laminate or the device according to the present application, it is possible to finely adjust the optical properties step by step.

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.

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.

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.

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

Experimental Example  One: Metal oxynitride layer Translucent  Confirm

Production Example  One

Preparation of the laminate : ITO having a light transmittance of about 90% was formed on one surface of glass (galss) having a light transmittance of about 98%. Subsequently, 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. Specifically, 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.

Physical property measurement: The content ratio of each element of the oxynitride layer and the transmittance of the laminate were measured, and are shown in Table 1 below. Elemental content (atomic%) was measured by X-ray photoelectron spectroscopy (XPS), and transmittance was measured using a haze meter (solidspec 3700).

Production Example  2

During deposition, 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.

Production Example  3

During deposition, 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.

Production Example  4

When the deposition rate of nitrogen was 0 sccm, except that the content ratio was changed as shown in Table 1, an oxide layer was formed in the same manner as in Preparation Example 1.

TABLE 1

From Table 1, it can be inferred that 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.

Experimental Example  2: Metal oxynitride  Discoloration check

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 same measurements were also performed for ± 4 V and ± 5 V, and the results are shown in Table 2.

TABLE 2

As in Table 2, it can be confirmed that 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.

Experimental Example  3: conductivity Laminate  Comparison of driving time and available level of electrochromic device including the same

Example  One

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. At this time, 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.

Subsequently, a laminate of Prussian blue (PB) and ITO was bonded to the conductive laminate through a GPE (gel polymer electrolyte) in the form of a film. 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).

Comparative example  One

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).

It can be seen from FIG. 2 (b) that the driving of the comparative example device is limited to approximately 500 cycles. However, as shown in Figure 2 (a), it can be confirmed that even if the device of the embodiment is driven 2.5 times or more compared to the comparative example, no performance degradation was observed. This is the Mo _a Ti _b O _x N _y of the example device The layer is judged to be the result of improving the durability of the device by preventing deterioration of adjacent OMO or WO ₃ .

On the other hand, with respect to the electrochromic device, 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. Unlike the comparative example, 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.

Experimental Example  4: conductive Laminate  And discoloration time of the electrochromic device comprising the same

Example  2

Using a Solidspec 3700 equipment, the amount of charge and the current of the device were measured at the time when the change in the discoloration of some of the experiments performed in Example 1. The result is shown in FIG. 3 (a). In the graph of FIG. 3 (a), the X axis represents time.

Comparative example  2

For the device of Comparative Example 1, the charge amount and the current of the device were measured in the same manner as in Example 2. The result is shown in FIG. 3 (b).

Unlike FIG. 3 (b), 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.

Experimental Example  4: conductive Laminate  And check the fine transmittance control function of the electrochromic device including the same

Example  3

For the device of Example 1, -1 V, -2 V, and -3 V were applied stepwise as the coloring level, and 0.5 V as the discoloration potential. The transmittance and color at each voltage measured using the Solidspec 3700 device are shown in Table 3 and FIG. 4.

TABLE 3

From Table 3 and FIG. 4, 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. In this case, it can be confirmed that the light blocking property is very high. Specifically, since -1 V is applied, the metal oxide layer including WO ₃ is colored in light blue, and after -2 V is applied, 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).

Claims (20)

1. A metal oxynitride layer, a metal oxide layer, and a conductive layer,

   A conductive laminate in which a monovalent cation is present in the metal oxynitride layer or the metal oxide layer.
2. The conductive laminate of claim 1, wherein monovalent cations are present in the metal oxynitride layer and the metal oxide layer.
3. The process according to any one of the preceding claims, characterized in that the metal oxynitride layer 5.0 × 10 per cm ^{2 - 9} mol to 5.0 × 10 ^{- 7} mol 1 is 1.0 × 10 per there is a cation, and the metal oxide layer cm ² of the ^- A conductive laminate in which ⁸ mol to 1.0 × 10 ^-6 mol of monovalent cation is present.
4. The conductive laminate of claim 1, wherein the monovalent cation is H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ .
5. The conductive laminate according to claim 1, wherein the visible light transmittance of the conductive laminate is 45% or less.
6. The conductive laminate of claim 1, wherein the metal oxide layer comprises a reducing color change material or an oxidative color change material.
7. The conductive laminate of claim 6, wherein the reducing discoloration material comprises an oxide of Ti, Nb, Mo, Ta, or W. 8.
8. 8. The conductive laminate according to claim 7, wherein the metal oxynitride layer has an oxynitride containing two or more metals selected from Ti, Nb, Mo, Ta, and W.
9. The conductive laminate of claim 8, wherein the metal oxynitride layer includes Mo and Ti.
10. The conductive laminate of claim 9, wherein the metal oxynitride layer is represented by Formula 1 below:

    [Formula 1]

    Mo _a Ti _b O _x N _y

    (Where 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, and a> 0 , b> 0, x> 0, y> 0, 0.5 <a / b <4.0, and 0.005 <y / x <0.02.)
11. The conductive laminate according to claim 1, wherein the metal oxynitride layer has a thickness of 150 nm or less.
12. The conductive laminate of claim 1, wherein the conductive layer comprises a transparent conductive compound, a metal mesh, or an oxide / metal / oxide (OMO).
13. The method of claim 12, wherein the oxide / metal / oxide (OMO) comprises an upper layer and a lower layer, wherein the upper and lower layers are Sb, Ba, Ga, Ge, Hf, In, La, Se, Si, Ta, Se, A conductive laminate comprising an oxide of Ti, V, Y, Zn, Zr or these alloys.
14. The conductive layer of claim 13, wherein the upper layer has a thickness ranging from 10 nm to 120 nm and a visible refractive index ranging from 1.0 to 3.0, and the lower layer has a thickness ranging from 10 nm to 100 nm and a visible refractive index ranging from 1.3 to 2.7. Laminate.
15. The conductive laminate of claim 13, wherein the oxide / metal / oxide (OMO) includes a metal layer between the upper layer and the lower layer, and the metal layer includes Ag, Cu, Zn, Au, Pd, or an alloy thereof. .
16. The conductive laminate of claim 15, wherein the metal layer has a thickness ranging from 3 nm to 30 nm and a visible light index of refraction of 1 or less.
17. The conductive laminate according to claim 1; An electrolyte layer; And a counter electrode layer sequentially including the counter electrode layer.
18. The electrochromic device of claim 17, wherein the electrolyte layer comprises a compound providing H ⁺ , Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , or Cs ⁺ .
19. The electrochromic device of claim 17, further comprising an ion storage layer between the counter electrode layer and the electrolyte layer.
20. The electrochromic device of claim 19, wherein the ion storage layer comprises a color change material having a color development property different from that of a color change material included in the metal oxide layer.

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