KR102101151B1 - An Electrochromic Device - Google Patents

Abstract

The present application relates to an electrochromic device and its manufacturing method. The present application, which includes a novel ion storage layer material and an electrochromic material, provides an electrochromic device having excellent durability and thin film productivity, and an improved discoloration rate compared to the prior art.

Description

An electrochromic device

The present application relates to an electrochromic device.

Electrochromism refers to a phenomenon in which optical properties such as color or light transmittance of an electrochromic active material change according to an electrochemical oxidation and reduction reaction. The electrochromic device using this phenomenon can be manufactured as a device having a large area at a low cost, and because of low power consumption, it has attracted attention in various fields such as smart windows, smart mirrors, and electronic paper.

1 shows a cross-section of a typical electrochromic device. As shown in the figure, the electrochromic device 100 includes a first electrode layer 110, an electrochromic layer 120 provided on the first electrode layer, an electrolyte layer 130 provided on the electrochromic layer, and an electrolyte layer. It may include an ion storage layer 140 provided on, and a second electrode layer 150 provided on the ion storage layer. Although not shown, a substrate formed from a transparent glass or a polymer resin may be additionally included on the outer surface of each electrode 110 or 150.

In general, the electrochromic layer and / or the ion storage layer may include an inorganic material such as tungsten oxide (WO _x ) or lithium nickel oxide (LiNiO _x ) as an electrochromic material. When a voltage is applied to the device, the color of the electrochromic material may be changed. Specifically, when a specific potential is applied to the electrode, electrolyte ions such as H ⁺ , or Li ⁺ , Na ⁺ move between the electrochromic layer and the ion storage layer through the electrolyte layer, and at the same time, electrons are transferred through an external circuit. As it is injected into the discoloration layer or detached from the electrochromic layer, the electrochromic material is oxidized or reduced, and as a result, coloring or discoloration of the electrochromic layer or ion storage layer is achieved. As described above, since the movement of electrolyte ions is assumed to change the optical properties of the electrochromic device, discoloration takes a predetermined time, that is, a switching time, thereby reducing the discoloration time and improving discoloration efficiency. Skill is required.

One object of the present application is to provide an electrochromic device having improved discoloration speed and excellent discoloration efficiency.

Another object of the present application is to provide an electrochromic device having a sufficient discoloration effect even with a thin film.

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

The present application relates to an electrochromic device. The electrochromic device may include two opposing electrode layers, an electrochromic layer, an electrolyte layer, and an ion storage layer.

The electrode may mean a configuration capable of supplying electric charge to the electrochromic layer. In one example, the electrode may be formed of any one or more of a transparent conductive oxide (Transparent Conductive Oxide, TCO), a conductive polymer, silver nanowires (Ag Nanowire), or a metal mesh (Metal mesh). More specifically, ITO (Indium Tin Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium doped Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), IZO (Indium doped Zinc Oxide) , NTO (Niobium doped Titanium Oxide), ZnO, OMO (Oxide / Metal / Oxide) or CTO may be used as an electrode material, but is not limited thereto. In another example, the electrode layer may have a structure in which two or more electrode materials are stacked in a plurality of layers.

The method of forming the electrode layer is not particularly limited, and a known method can be used without limitation. For example, an electrode layer may be provided by forming an electrode material including transparent conductive oxide particles in a thin film form on a transparent glass substrate through a sputtering process. The electrode layer may have a thickness of 150 nm or more, 200 nm or more, or 300 nm or more within a range of 1 nm to 1 μm. The upper limit of the thickness of the electrode layer is not particularly limited, but in order to achieve low resistance, the electrode layer may have a thickness of 800 nm or less, 700 nm or less, or 500 nm or less.

In one example, the electrode layer may have a light transmittance in the range of 70% to 95% with respect to visible light. In the present application, visible light may mean light having a wavelength in a range of about 350 nm to 750 nm, and more specifically, light having a wavelength of 550 nm.

The electrochromic layer may include an electrochromic material whose color changes according to an electrical signal. Electrochromic materials that can be used include conductive polymers, organic colorants, and / or inorganic colorants. Examples of the conductive polymer include polypyrrole, polyaniline, polypyridine, polyindole, polycarbazole, and the like, and examples of the organic color change material include materials such as viologen, anthraquinone, and phenocyazine.

In the case of the prior art, as the electrochromic material, inorganic oxides such as tungsten oxide (WO _x ) are mainly used. However, since inorganic oxides such as tungsten oxide (WO _x ) have poor thin film formation efficiency, there is a problem that productivity decreases. Specifically, in order to secure a sufficient discoloration effect when forming an electrochromic layer using tungsten oxide (WO _x ), not only a large reaction area but also a sufficient thickness around 400 nm was required. Since the rate of movement of ions decreases with increasing, the discoloration rate of the electrochromic device is slowed. In view of this problem of the prior art, the present application includes copper nitride (CuN _x ) as an electrochromic material. As mentioned below, copper nitride (CuN _x ) has excellent thin film deposition productivity and can exhibit a sufficient electrochromic effect even at a thickness of 150 nm or less.

In one example, the electrochromic layer including copper nitride may have a deep blue color by coloring when a voltage having a size of 2.5 V or more is applied. For example, when a negative voltage having a size exceeding 2.5 V is applied, an electrolyte layer such as Li ⁺ is inserted into the electrochromic layer containing copper nitride, and the electrochromic layer has a deep blue color. In this case, the electrochromic layer may have light transmittance for visible light in the range of 40% to 55%. Conversely, after coloring, when a positive (+) voltage having a size of 2 V or less is applied to the electrochromic layer containing copper nitride, the electrochromic layer may be discolored, wherein the electrochromic layer is 65% to It may have a light transmittance for visible light in the range of 75%.

In one example, the copper nitride (CuN _x ) may be copper nitride having a mass ratio of copper and nitrogen of 0.01 ≤ N / Cu ≤ 0.3. More specifically, copper nitride having a range of 0.05 ≤ N / Cu ≤ 0.2 may be used. When the mass ratio of the N / Cu exceeds 0.2, it is difficult to prepare an electrochromic layer because the copper nitride thin film is thermodynamically unstable, and when the mass ratio is less than 0.05, it is difficult to impart transparency to the thin film because the metal properties dominate.

Although not particularly limited, in one example, the electrochromic layer including copper nitride may have a refractive index for visible light in the range of 1.0 to 3.0.

In one example, the electrochromic layer comprising copper nitride may have a sheet resistance in the range of 1,000 Ω / □. When the range resistance value is satisfied, the response speed of the device can be increased and the switching time can be reduced.

In one example, the electrochromic layer containing copper nitride may have a thickness of 10 nm to 150 nm, 100 nm or less, 80 nm or less, or 50 nm or less. When the thickness is less than 10 nm, a color change reaction is difficult to occur sufficiently, and when it exceeds 150 nm, an electrochromic device of a thin film cannot be provided and productivity may be deteriorated.

The ion storage layer may mean a layer capable of participating in a discoloration reaction because charge particles required for the redox reaction of the electrochromic layer can be inserted or removed. In the prior art, in order to balance the charge between the electrochromic layer and the ion storage layer, complementary electrochromic materials were used in each of the electrochromic layer and the ion storage layer. For example, when the electrochromic layer contains an oxidative discoloration material such as lithium nickel oxide (LiNiO _x ), the ion storage layer contains a reductive discoloration material such as tungsten oxide (WO _x ). However, the electrochromic device having the above-described configuration has a disadvantage that the discoloration efficiency is not good and the switching time is slow.

In consideration of the problems of the prior art, the electrochromic device according to the present application uses an ion storage layer containing conductive graphite. The conductive graphite having a unique structure and high strength due to it can prevent cracking of the ion storage layer and improve durability of the device. In addition, the layered structure of graphite can provide a space in which electrolyte ions involved in electrochromic discoloration can be sufficiently inserted and desorbed. Furthermore, since the conductive graphite has excellent thin film deposition properties and can sufficiently store and store charges even at a thickness of 100 nm or less, it is possible to reduce the switching time required between discoloration and decolorization of the device.

The conductive graphite may be graphite oxide. In one example, the graphite oxide may have an oxygen to carbon mass ratio of 0.001 ≤ O / C ≤ 0.5, or 0.005 ≤ O / C ≤ 0.3. Specifically, when XPS analysis of the distribution of the constituent elements of the graphite thin film, the content of the C element and the O element may be slightly different depending on the measurement position, but as a whole thin film, graphite satisfying the above range may be used. When the mass ratio is less than 0.005, the conductivity is somewhat improved, but the transmittance decreases, and if it exceeds 0.3, the electrical conductivity may decrease.

In one example, the ion storage layer of the present application may be formed in a thickness of 10 nm to 150 nm, 100 nm or less, or 80 nm or less. If the thickness is less than 10 nm, the ion storage effect is insufficient, and when it exceeds 150 nm, a transparent ion storage layer of a thin film cannot be provided and productivity may be deteriorated.

In another example, the refractive index of the ion storage layer with respect to visible light may range from 1.0 to 3.0.

In one example, an ion storage layer formed by depositing graphite on an electrode may greatly reduce internal resistance to ion migration. For example, in the case of an ion storage layer formed from a conventional lithium nickel oxide, the internal resistance showed a range of 1M Ω / □ to 10M Ω / □, whereas in the case of an ion storage layer formed by depositing graphite, the internal resistance was 100 Ω / Since it has a range of □ to 1,000 Ω / □, it can contribute to shortening of discoloration time.

In addition, in one example, the ion storage layer may have a visible light transmittance in the range of 65% to 75%.

The electrolyte layer may include ions involved in the electrochromic reaction, such as lithium ions (Li ⁺ ). The type of electrolyte contained in the electrolyte layer is not particularly limited, and a liquid electrolyte, a gel-polymer electrolyte, or an inorganic solid electrolyte may be used.

In one example, when the electrolyte is a gel-polymer electrolyte, the electrolyte layer may include a cured product of a composition comprising a carbonate compound and a lithium compound. Since the carbonate-based compound has a high dielectric constant, it is possible to increase the conductivity of ions provided by the lithium salt. For example, carbonate-based compounds such as propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC) may be used, but are not limited thereto. In addition, LiF, LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiClO ₃ , LiAsF ₆ , LiSbF ₆ , LiAl0 ₄ , LiAlCl ₄ , LiNO ₃ , LiN (CN) ₂ , LiPF ₆ , Li (CF ₃ ) ₂ PF ₄ , Li (CF ₃ ) ₃ PF ₃ , Li (CF ₃ ) ₄ PF ₂ , Li (CF ₃ ) ₅ PF, Li (CF ₃ ) ₆ P, LiSO ₃ CF ₃ , LiSO ₃ C ₄ F ₉ , LiSO ₃ (CF ₂ ) ₇ CF ₃ , LiN (SO ₂ CF ₃ ) ₂ , and the like, but are not limited thereto.

In another example, when the electrolyte is an inorganic solid electrolyte, the electrolyte layer may include lithium phosphorus oxynitride, so-called Lithium Phosphorous Oxynitride (LIPON), or for example, Ta ₂ O ₅ To oxides of transition metals It may include an electrolyte doped with lithium ions. Examples of the transition metal that can be used in the inorganic solid electrolyte include transition metals such as molybdenum (Mo), tantalum (Ta), zirconium (Zr), hafnium (Hf), and tungsten (W). In the case of the gel polymer, as the charge / discharge cycle increases, the bubble is generated and its durability is lowered, whereas when using the inorganic solid electrolyte, since there is no bubble generation, the durability and life of the device can be increased.

The electrolyte layer may have a thickness in the range of 30 μm to 200 μm, and the transmittance to visible light may range from 70% to 95%.

The electrochromic device of the present application may further include a power source. For example, the power source may be electrically connected to the electrode layer through an external circuit. The device or method for applying the voltage may be appropriately selected by those skilled in the art and is not particularly limited.

In one example, the power source can apply an asymmetrical discoloration potential. More specifically, the power source may apply a coloring potential having a size of 2.5 V or more to the electrochromic device, and a decolorizing potential having a size of 2 V or less. In the case of the present application, only the electrochromic layer is colored or decolored depending on the voltage applied, and the ion storage layer may have a light transmittance in a certain range without coloring or decoloring. For example, when a negative voltage of more than 2.5V is applied to a layer containing copper nitride, that is, an electrode layer on which an electrochromic layer is directly stacked, an electrochromic layer is colored and the electrochromic layer is colored. During the time (duration time), the conductive graphite contained in the ion storage layer may function as an ion storage layer while maintaining transparency without discoloration. Conversely, in order for the electrochromic device to decolor, a positive potential having a size of 2 V or less must be applied to the electrode layer on which the electrochromic layer containing copper nitride is directly stacked. When the coloring potential is less than 2.5 V, copper nitride (CuN _x ) is not discolored, and thus, discoloration and discoloration of the device cannot be caused. When the voltage in the above range is applied, irrespective of the decolorization reaction of the electrochromic layer, the ion storage layer can maintain a transmittance in the range of 65% to 75% with respect to visible light without a large change in optical properties.

In another example of the present application, the present application relates to a method of manufacturing an electrochromic device. More specifically, the manufacturing method includes: providing a copper nitride layer having a mass ratio of copper and nitrogen on a single electrode layer in a range of 0.05 ≤ N / Cu ≤ 0.2; And providing a graphite layer having a mass ratio of oxygen and carbon in the range of 0.005 ≤ O / C ≤ 0.3 on the other electrode layer. As described above, the copper nitride layer is an electrochromic layer, and the graphite layer can be used as an ion storage layer. The structure of the electrode layer, the ion storage layer, and the electrochromic layer or other characteristics are the same as those mentioned above.

The method of providing each layer is not particularly limited, and a known method can be used. For example, any one of deposition, spin coating, dip coating, screen printing, gravure coating, sol-gel method, or slot die coating method Each layer can be provided by. In the case of deposition, it may be made by physical vapor deposition (PVD) or chemical vapor deposition (CVD). Available physical vapor deposition methods include sputtering, e-beam evaporation, thermal evaporation, laser molecular beam epitaxy (L-MBE), or pulsed laser deposition ( Examples include Pulsed Laser Deposition (PLD), and chemical vapor deposition methods include Thermal Chemical Vapor Deposition, Plasma-Enhanced Chemical Vapor Deposition (PECVD), and Photochemical Vapor Deposition (Light). Examples include Chemical Vapor Deposition, Laser Chemical Vapor Deposition, Metal-Organic Chemical Vapor Deposition (MOCVD), or Hydride Vapor Phase Epitaxy (HVPE). However, it is not limited thereto.

In one example, a copper nitride layer or a graphite layer may be deposited on each electrode layer by sputtering. More specifically, in the case of the copper nitride layer, a Cu target having a thickness of approximately 30 to 60 nm is formed, and in a chamber having a process pressure of 5 mTorr to 60 mTorr, power of 100 W to 300 W is applied, and nitrogen A copper nitride layer may be provided on the electrode layer through a process of supplying (N ₂ ) gas and argon (Ar) gas at a flow rate of 5 sccm to 25 sccm and 15 sccm to 45 sccm, respectively. At this time, the partial pressure ratio (N / Ar) of nitrogen and argon supplied into the chamber is not particularly limited, but may be 40% or more. In addition, in the case of the graphite layer, argon (Ar) 100% atmosphere, 5 mTorr to 25 mTorr process pressure and 200 W of power can be deposited and formed for 2,000 sec.

The manufacturing method of the present application may further include providing a solid electrolyte layer on one surface of the copper nitride layer or the graphite layer. The types of electrolytes that can be used in the electrolyte layer are the same as those mentioned above.

The present application, which includes a novel ion storage layer material and an electrochromic layer material, can provide an electrochromic device with excellent thin film productivity and improved discoloration efficiency and discoloration rate.

1 schematically shows a cross-sectional view of a typical electrochromic device.

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 1: Measurement of the optical and driving characteristics of a half-cell

For the half-cells prepared as follows, the driving characteristics and optical characteristics of each cell were measured at a temperature of 25 ° C. using a potentiostat equipment (Princeton Applied Research, PMC-1000) and a UV-vis spectrometer equipment (Solidspec 3700). . A voltage of -3V was applied to the half-cell as a coloring potential, and a voltage of + 2V was applied to the discoloring potential. The size of each specimen used was matched with 2.0 cm X 10 cm = 20 cm ² . The results are shown in Table 1 below.

Example

Preparation of working electrode: On a transparent conductive oxide ITO electrode, an electrochromic layer formed of copper nitride (CuNx) is deposited to a thickness of 30 nm using a DC sputter method, and a working electrode including a first electrode and an electrochromic layer is prepared. It was prepared.

Preparation of counter electrode: On the ITO electrode, which is a transparent conductive oxide, a DC storage method is used to deposit a formed ion storage layer containing conductive graphite to a thickness of 50 nm, and a working electrode including a second electrode and an ion storage layer is prepared. Did.

Comparative example

The electrochromic layer is different from the same as in the above embodiment, except that a 300 nm thick tungsten oxide (WOx) layer is used, and a 100 nm thick lithium nickel oxide (LiNiOx) layer is used as the ion storage layer. An electrochromic layer and an ion storage layer were prepared on the ITO electrode using a DC sputter method.

Comparison of Half-Cell Optical and Driving Characteristics Half-cell: working electrode including electrochromic layer Half-cell: counter electrode including ion storage layer Measure
Item TCO sheet resistance
(Ω / □) Charge
(mC) △ T (%) Time (s)
Col. / Ble. TCO sheet resistance Charge
(mC) △ T (%) Time (s)
Col. / Ble. Example 30 50 25 10/10 30 50 - - Comparative example 30 600 60 60/30 30 200 40 30/30 TCO sheet resistance: sheet resistance value of ITO electrode
△ T: Difference in transmittance during coloring and decolorization of each electrode
Time (s) Col. : Time required for the electrode to switch from a bleaching state to a coloring state. It can be measured as the time required to have 80% transmittance compared to the transmittance of the fully colored state.
Time (s) Ble. : The time required for the electrode to change from a coloring state to a coloring state. It can be measured as a time required to have a transmittance of 80% compared to a transmittance of a completely discolored state.

As shown in Table 1, it can be seen that the electrochromic layer included in the working electrode of the present application can shorten the coloring and decoloring time when compared with the electrochromic layer of the comparative example.

In addition, it can be confirmed that the ion storage layer included in the counter electrode of the present application has no change in transmittance, unlike the ion storage layer of the comparative example. This means that in the case of the lithium nickel oxide included in the ion storage layer of the comparative example, coloring and decoloring occurs depending on the applied voltage, whereas the graphite included in the ion storage layer of the example does not cause coloring and decoloring.

Experimental Example 2: Measurement of optical and driving characteristics of full-cell

The working electrode and the counter electrode prepared in each of the above Examples and Comparative Examples were bonded through a gel polymer electrolyte prepared from a mixture of PC (propylene carbonate) and LiClO ₄ to prepare an electrochromic device. About the prepared electrochromic device, optical and driving characteristics were measured using the same apparatus as Experimental Example 1. The results are shown in Table 2 below.

Comparison of Full-Cell Optical and Driving Characteristics Electrochromic device (full cell) △ T (%) Coloring Time (s) Bleaching Time (s) Charge amount (mC) Example 25 10 5 50 Comparative example 50 36 13 250 △ T: Difference in transmittance during coloring and decoloring of all devices
Bleaching Time (s): Time required when the electrochromic layer is bleaced in the coloring state. It can be measured as a time required to have a transmittance of 80% compared to a transmittance of a completely discolored state.
Coloring Time (s): The time required when the electrochromic layer is colored in a bleacing state. It can be measured as the time required to have 80% transmittance compared to the transmittance of the fully colored state.

As shown in Table 2, it can be seen that the electric charge amount of the entire electrochromic device composed of the working electrode and the counter electrode is larger in that of the comparative example. However, in the case of discoloration efficiency (coloration efficiency = DELTA T / charge amount), which can be expressed by a change in transmittance with respect to the amount of charge, it can be seen that the device of the embodiment is significantly higher than the device of the comparative example. Furthermore, it can be seen that the device of the embodiment has a switching time shortened by 50% or more compared to the comparative example.

Claims (21)

It is an electrochromic device comprising two electrode layers, electrochromic layer, ion storage layer, and electrolyte layer disposed opposite to each other, the electrochromic layer includes copper nitride (CuN _x ), and the ion storage layer includes conductive graphite. Electrochromic device.
The electrochromic device of claim 1, wherein the conductive graphite is graphite oxide, and the mass ratio of oxygen and carbon is in the range of 0.005 ≤ O / C ≤ 0.3.
The electrochromic device of claim 2, wherein the ion storage layer has a resistance of 100 Ω / □ to 1,000 Ω / □.
The electrochromic device of claim 2, wherein the ion storage layer has a thickness in a range of 10 nm to 150 nm, and a refractive index of visible light in a range of 1.0 to 3.0.
The electrochromic device of claim 2, wherein the ion storage layer has a transmittance of 65% to 75% of visible light.
The electrochromic device of claim 1, wherein the copper nitride (CuN _x ) has a mass ratio in the range of 0.05 ≤ N / Cu ≤ 0.2.
The electrochromic device of claim 6, wherein the electrochromic layer has a resistance of 1,000 Ω / □ or less.
The electrochromic device of claim 6, wherein the electrochromic layer has a thickness in the range of 10 nm to 150 nm, and a refractive index of visible light in the range of 2.0 to 3.5.
The electrochromic device of claim 6, wherein the electrochromic layer has a transmittance of 40% to 55% for visible light when colored, and a transmittance of 65% to 75% for visible light when discolored.
The electrochromic device of claim 1, wherein the electrolyte layer has a thickness of 30 μm to 200 μm, and a light transmittance to visible light in a range of 70% to 95%.
The electrochromic device according to claim 1, wherein the electrolyte layer comprises any one of a liquid electrolyte, a gel-type polymer electrolyte, or an inorganic solid electrolyte.
The electrochromic device of claim 11, wherein the electrolyte is an inorganic solid electrolyte containing LiPON or Ta ₂ O ₅ .
The electrochromic device according to claim 11, wherein the electrolyte is a gel-type polymer electrolyte formed from a cured product of a mixture containing a carbonate compound and a lithium compound.
The electrochromic device according to claim 13, wherein the carbonate-based compound is selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate (EMC).
The method of claim 13, wherein the lithium compound is LiF, LiCl, LiBr, LiI, LiClO ₄ , LiBF ₄ , LiClO ₃ , LiAsF ₆ , LiSbF ₆ , LiAl0 ₄ , LiAlCl ₄ , LiNO ₃ , LiN (CN) ₂ , LiPF ₆ , Li (CF ₃ ) ₂ PF ₄ , Li (CF ₃ ) ₃ PF ₃ , Li (CF ₃ ) ₄ PF ₂ , Li (CF ₃ ) ₅ PF, Li (CF ₃ ) ₆ P, LiSO ₃ CF ₃ , LiSO ₃ Electrochromic device selected from C ₄ F ₉ , LiSO ₃ (CF ₂ ) ₇ CF ₃ , and LiN (SO ₂ CF ₃ ) ₂ .
According to claim 1, The electrode layer, ITO (Indium Tin Oxide), FTO (Fluor doped Tin Oxide), AZO (Aluminium doped Zinc Oxide), GZO (Galium doped Zinc Oxide), ATO (Antimony doped Tin Oxide), IZO ( At least one transparent conductive compound (TCO) selected from the group consisting of Indium doped Zinc Oxide (NTO), Niobium doped Titanium Oxide (NTO), ZnO, Oxide / Metal / Oxide (OMO) and CTO; Conductive polymers; Ag nanowire; And a metal mesh.
The electrochromic device of claim 16, wherein the electrode layer has a thickness in a range of 1 nm to 1 μm, and a transmittance to visible light is in a range of 70% to 95%.
According to claim 1, wherein the electrochromic device further includes a power source, the color dislocation of the electrochromic device is a negative (-) potential having a size of 2.5V or more, and the decolorization potential is an amount of 2V or less ( Electrochromic element which is the potential of +).
Providing a copper nitride layer having a mass ratio of copper and nitrogen in the range of 0.05 ≤ N / Cu ≤ 0.2 on one electrode layer; And
A method of manufacturing an electrochromic device comprising the step of providing a graphite layer having a mass ratio of oxygen and carbon in the range of 0.005 ≤ O / C ≤ 0.3 on another electrode layer.
20. The method of claim 19, wherein the copper nitride layer or graphite layer is deposited (deposition), spin coating (spin coating), dip coating (dip coating), screen printing, gravure coating, sol-gel (sol-Gel) method, or slot die Method of manufacturing an electrochromic device provided by any one of the coating (slot die) method.
The method of claim 19, further comprising the step of providing a solid electrolyte layer on one surface of any one of the copper nitride layer or the graphite layer, the solid electrolyte layer comprises a gel-polymer electrolyte or an inorganic solid electrolyte Method for manufacturing electrochromic device.

Images