Ion storage layer for electrochromic device, method for manufacturing the same, and electrochromic device including the same

Abstract

A method for manufacturing an ion storage layer for an electrochromic device is provided, comprising the steps of: forming a transparent conductive layer on a substrate; and simultaneously providing on the conductive layer an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material.

Description

Technology Field

[0001] The present application relates to an ion storage layer for an electrochromic device, a method for manufacturing the same, and an electrochromic device comprising the same. More specifically, it relates to an ion storage layer for an electrochromic device in which electrochromic performance, electrochemical performance, structural stability, mechanical durability, long-term stability, lifespan, transmittance, and modulation rate are improved through an auxiliary material doped into an ion storage material that contributes to electrochromism through oxidation and reduction reactions, a method for manufacturing the same, and an electrochromic device comprising the same.

[0003] This application is derived as a result of the following research and development project.

[0004] Industry-Academic Cooperation Foundation Project No.: S-2024-1768-008

[0005] Research Project Name: Gyeonggi Regional Cooperation Research Center (GRRC) Project

[0006] Research Project Title: [Applied 2-Gyeonggi-do] Development of PVD-based soft deposition process technology

[0007] Project Period: July 1, 2023 – June 30, 2026

[0008] Years of experience: 3rd year

[0009] Manager: Kim Han-ki

[0010] Funding Agency: Local Government) Local Autonomy-Gyeonggi Regional Cooperation Research Center (GRRC) (2016) Background Technology

[0012] Electrochromic (EC) smart windows can operate at low power and / or low voltage, and when combined with solar power, can reduce heating and cooling energy consumption by more than 30%.

[0013] Accordingly, electrochromic (EC) smart windows are attracting attention as a next-generation energy-saving technology.

[0014] As a result, electrochromic (EC) smart windows can be utilized in various fields such as eco-friendly construction, the automotive industry, and the aerospace industry; accordingly, research is actively being conducted to improve the performance and ensure the durability of electrochromic (EC) devices. For example, Korean Registered Patent Publication No. 10-2078222 describes adding or adsorbing a ligand substance to a reductive colorimetric material, a semiconductor material, and an electron transporter, or adding or adsorbing a ligand substance to a reductive colorimetric material and a semiconductor material, or adding or adsorbing a ligand substance to a reductive colorimetric material and a semiconductor material and mixing an electron transporter, or adding or adsorbing a ligand substance to a semiconductor material and an electron transporter and mixing a reductive colorimetric material, or adding or adsorbing a ligand substance to a reductive colorimetric material and an electron transporter and mixing a semiconductor material, or adding or adsorbing a ligand substance to a semiconductor material and mixing a reductive colorimetric material, or adding or adsorbing a ligand substance to a semiconductor material and mixing a reductive colorimetric material and an electron transporter, or adding or adsorbing a ligand substance to a reductive colorimetric material and mixing a semiconductor material, or adding or adsorbing a ligand substance to a reductive colorimetric material and mixing a semiconductor material, or to an electron transporter A method for manufacturing a photosensitive autochromic precursor is disclosed, characterized by including the step of preparing a reduction-chromic mixture that changes color through photosensitivity by adding or adsorbing a ligand material and mixing a reduction-chromic material, or by adding or adsorbing a ligand material to an electron transporter and mixing a reduction-chromic material and a semiconductor material.As another example, Korean Registered Patent Publication No. 10-1731301 describes an electrochromic device comprising a reduction-chromic layer, an electrolyte layer, and an oxidation-chromic layer, wherein the method comprises the steps of: laminating a porous polymer membrane on the reduction-chromic layer; applying a reactive electrolyte solution on the porous polymer membrane to form an electrolyte layer filled with the reactive electrolyte solution inside the porous polymer membrane; laminating an oxidation-chromic layer on the electrolyte layer; and irradiating the laminated electrochromic device with light to gel the reactive electrolyte solution, wherein the reactive electrolyte solution is a mixture composed of an electrolyte salt, an organic solvent, a crosslinking agent containing a photocuring group, a photoinitiator, and an additive, wherein the crosslinking agent is ethylene glycol di(meth)acrylate, poly(ethylene glycol) di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, tri(propylene glycol) di(meth)acrylate, trimethylolpropane tri(meth)acrylate, A method for manufacturing an electrochromic device is disclosed, wherein the mixture is one or more mixtures selected from the group consisting of pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, and the additive is one or more selected from ionic liquids, Lewis acids, leveling agents, silane coupling agents, or mixtures thereof, and the crosslinking agent and the photoinitiator undergo a photocuring reaction through the light irradiation to form a gel polymer electrolyte.

[0015] However, conventional electrochromic (EC) devices may have limitations in that structural and electrochemical degradation of the ion storage layer occurs during long-term electrochromic (EC) cycle operation.

[0016] In particular, conventional electrochromic (EC) devices may have limitations in mechanical stability when applied as flexible devices.

[0017] In addition, conventional electrochromic (EC) devices may have a limitation in that their performance degrades rapidly after repeated fatigue bending tests.

[0018] Accordingly, there is a need for a new method for manufacturing ion storage layers that can simultaneously improve electrochemical stability and mechanical durability while ensuring applicability to flexible devices. The problem to be solved

[0020] The technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device having excellent electrochromic performance, a method for manufacturing the same, and an electrochromic device including the same.

[0021] Another technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device with excellent electrochemical performance, a method for manufacturing the same, and an electrochromic device including the same.

[0022] Another technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device having excellent structural stability, a method for manufacturing the same, and an electrochromic device including the same.

[0023] Another technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device with excellent mechanical durability, a method for manufacturing the same, and an electrochromic device including the same.

[0024] Another technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device with high long-term stability and a long lifespan, a method for manufacturing the same, and an electrochromic device including the same.

[0025] Another technical problem that the present application aims to solve is to provide an ion storage layer for an electrochromic device having a fast response speed and excellent transmittance and modulation rate, a method for manufacturing the same, and an electrochromic device including the same.

[0026] The technical problems that this application aims to solve are not limited to those described above. means of solving the problem

[0028] To solve the above technical problem, the present application provides a method for manufacturing an ion storage layer for an electrochromic device.

[0029] According to one embodiment, the method for manufacturing an ion storage layer for an electrochromic device may include the steps of: forming a transparent conductive layer on a substrate; and simultaneously providing an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material on the conductive layer, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material.

[0030] According to one embodiment, the step of forming the ion storage thin film comprises controlling the doping concentration of the auxiliary material through magnetron sputtering, wherein in the magnetron sputtering, the auxiliary target containing the auxiliary material may be provided with a target power of more than 50 W and less than 100 W simultaneously with the ion storage target containing the ion storage material.

[0031] According to one embodiment, in the magnetron sputtering, the ion storage target can be provided with a target power of more than 150 W and less than 250 W simultaneously with the auxiliary target.

[0032] According to one embodiment, the ion storage thin film may be formed with a thickness of more than 150 nm and less than 250 nm.

[0033] According to one embodiment, the auxiliary material is doped by ion substitution into the lattice of the ion storage material, and by doping with the auxiliary material, the crystal grain size of the ion storage material may be reduced and the growth direction of the ion storage material may be changed.

[0034] According to one embodiment, the ion storage material grows in the (111) plane, and the auxiliary material induces growth in the (200) plane, and the structure of the ion storage thin film can be stabilized by changing the growth direction.

[0035] According to one embodiment, the ion storage target comprises nickel oxide (NiO), the auxiliary target comprises molybdenum oxide (MoO3), the ion storage material comprises nickel oxide (NiO), the auxiliary material comprises molybdenum (Mo), and the ion storage thin film may comprise molybdenum-doped nickel oxide (Mo-doped NiO).

[0036] According to one embodiment, in the ion storage thin film, Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ As it increases, electron density increases and electrical conductivity can be improved.

[0037] According to one embodiment, the method further includes the step of surface-modifying the substrate through ion beam treatment before forming the conductive layer, wherein the surface modification of the substrate strengthens the bonding strength between the surface-modified substrate and the conductive layer, and promotes the growth of the conductive layer and the ion storage thin film on the surface-modified substrate.

[0039] To solve the above technical problem, the present application provides an ion storage layer for an electrochromic device.

[0040] According to one embodiment, the ion storage layer for the electrochromic device comprises a substrate, a transparent conductive layer on the substrate, and an ion storage thin film on the conductive layer, wherein the ion storage thin film comprises an ion storage material and an auxiliary material doped into the ion storage material, and the ion storage material contributes to electrochromism through oxidation and reduction reactions, and the auxiliary material doped into the ion storage material can assist electrochromism by providing additional charge storage sites to the ion storage material.

[0041] According to one embodiment, the auxiliary material is doped by ion substitution into the lattice of the ion storage material, and can reduce the crystal grain size of the ion storage material and change the growth direction of the ion storage material.

[0042] According to one embodiment, the ion storage material comprises nickel (Ni), the auxiliary material comprises molybdenum (Mo), and the ion storage thin film may comprise molybdenum-doped nickel oxide (Mo-doped NiO).

[0043] According to one embodiment, in the ion storage thin film, Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ As it increases, electron density increases and electrical conductivity can be improved.

[0045] To solve the above technical problem, the present application provides an electrochromic device.

[0046] According to one embodiment, the electrochromic element may include an electrochromic layer, an ion storage layer comprising an ion storage material that contributes to the electrochromicity of the electrochromic layer through oxidation and reduction reactions, and an auxiliary material that is doped into the ion storage material to provide additional charge storage sites to the ion storage material and assist the electrochromicity.

[0047] According to one embodiment, the ion storage layer is Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ As it increases, electron density increases and electrical conductivity can be improved. Effects of the invention

[0049] According to an embodiment of the present application, a method for manufacturing an ion storage layer for an electrochromic device may be provided, comprising the steps of: forming a transparent conductive layer on a substrate; and simultaneously providing on the conductive layer an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material.

[0050] According to the method for manufacturing an ion storage layer for an electrochromic device according to an embodiment of the present application, an ion storage layer for an electrochromic device may be provided, comprising the substrate, the transparent conductive layer on the substrate, and the ion storage thin film on the conductive layer.

[0051] According to an embodiment of the present application, in the ion storage layer for the electrochromic device, the ion storage thin film may comprise the ion storage material and the auxiliary material doped into the ion storage material. The ion storage material contributes to electrochromism through oxidation and reduction reactions, and the auxiliary material doped into the ion storage material may assist the electrochromism by providing additional charge storage sites to the ion storage material.

[0052] According to an embodiment of the present application, in the ion storage layer for the electrochromic device, the auxiliary material is doped by ion substitution in the lattice of the ion storage material, and can reduce the crystal grain size of the ion storage material and change the growth direction of the ion storage material. The ion storage material tends to grow in the (111) plane, but the auxiliary material can induce growth in the (200) plane.

[0053] As a result, the growth direction of the ion storage thin film is changed, and the structure of the ion storage thin film can be stabilized.

[0054] As a result, the transmittance modulation of the ion storage layer for the electrochromic device is high and the response speed is fast, so the electrochromic performance of the ion storage layer for the electrochromic device can be excellent.

[0055] In addition, the charge storage capacity of the ion storage layer for the electrochromic device is large, and the electrolyte ion, for example, lithium ion (Li + Since the diffusion coefficient of ) is high, the electrochemical performance of the ion storage layer for the electrochromic device can be excellent.

[0056] In addition, the ion storage layer for the electrochromic device comprises a microstructure and a porous structure that facilitate ion diffusion, and through doping of the auxiliary material, the crystal grain size of the ion storage material is small and the lattice is shrunk, so that the structural stability of the ion storage layer for the electrochromic device can be excellent.

[0057] In addition, the ion storage layer for the electrochromic device has high flexibility, so the mechanical durability of the ion storage layer for the electrochromic device can be excellent.

[0058] In addition, the long-term stability of the ion storage layer for the electrochromic device is high, so the lifespan of the ion storage layer for the electrochromic device can be long.

[0059] In addition, the electronic conductivity of the ion storage layer for the electrochromic device is high, so the reaction speed of the ion storage layer for the electrochromic device is fast, and the transmittance and modulation rate can be excellent. Brief explanation of the drawing

[0061] FIG. 1 is a drawing for explaining a method for manufacturing an ion storage layer for an electrochromic device according to an embodiment of the present application. FIG. 2 is a drawing for explaining a substrate surface modification method according to an embodiment of the present application. FIG. 3 is a drawing for explaining a method for forming a conductive layer according to an embodiment of the present application. FIG. 4 is a drawing for explaining a substrate and a conductive layer according to an embodiment of the present application. FIG. 5 is a drawing for explaining a method for forming an ion storage thin film according to an embodiment of the present application. FIG. 6 is a diagram illustrating a grid of an ion storage material according to an embodiment of the present application. FIG. 7 is a diagram illustrating the growth direction of an ion storage material according to an embodiment of the present application. FIG. 8 is a diagram illustrating the grid of an ion storage material doped with an auxiliary material according to an embodiment of the present application. FIG. 9 is a diagram illustrating the changed growth direction of an ion storage material according to an embodiment of the present application. FIG. 10 is a drawing for explaining an ion storage layer for an electrochromic device according to an embodiment of the present application. FIG. 11 is a diagram illustrating ion beam treatment according to an experimental example of the present application. FIG. 12 is a diagram illustrating radio frequency (RF) magnetron sputtering according to an experimental example of the present application. FIG. 13 is the cyclic voltammetry (CV) measurement result of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application. FIG. 14 is the chronoaperometry (CA) measurement result of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application. Figure 15 shows the transmittance measurement results in the visible light region of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 16 is the chronoamperometric (CA) measurement result of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application. FIG. 17 is a field emission scanning electron microscope (FESEM) image of an ion storage thin film in an ion storage layer for an electrochromic device formed of nickel oxide (NiO) and experimental examples 1-1 to 1-7 of the present application. FIG. 18 is a cross-sectional field emission scanning electron microscope (FESEM) image of an ion storage thin film in an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 19 is an X-ray diffraction (XRD) graph of an ion storage thin film formed of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 20 is an X-ray diffraction (XRD) graph of an ion storage thin film in an ion storage layer for an electrochromic device according to Experimental Example 1-1 and Experimental Examples 1-3 to 1-7 of the present application. Figure 21 is the result of X-ray photoelectron spectroscopy (XPS) nickel (Ni) peak analysis of an ion storage thin film formed of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. Figure 22 is the result of X-ray photoelectron spectroscopy (XPS) molybdenum (Mo) peak analysis of an ion storage thin film in an ion storage layer for an electrochromic device according to Experimental Example 1-2 of the present application. Figure 23 is the result of energy dispersive spectroscopy (EDS) analysis of an ion storage thin film in an ion storage layer for an electrochromic device according to Experimental Example 1-2 of the present application. FIG. 24 is the cyclic voltammetry (CV) measurement result of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 25 is the result of electrochemical impedance spectroscopy (EIS) measurements of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 26 shows the long-term stability (a) transmittance and (b) current density measurement results of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 27 shows the bending critical limit and fatigue repetition test results of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 28 is a field emission scanning electron microscope (FESEM) image after a fatigue cycle test of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 29 shows the long-term stability (a) transmittance and (b) current density measurement results after a fatigue repetition test of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application. FIG. 30 shows the (a) cyclic voltammetry (CV) and (b) transmittance modulation measurements according to the oxygen partial pressure ratio at 550 nm of an ion storage layer for an electrochromic device according to Experimental Examples 2-1 to 2-3 of the present application. FIG. 31 shows the (a) cyclic voltammetry (CV) and (b) transmittance modulation measurements according to the oxygen partial pressure ratio at 550 nm of an ion storage layer for an electrochromic device according to Experimental Examples 3-1 to 3-3 of the present application. Specific details for implementing the invention

[0062] Hereinafter, preferred embodiments of the present application will be described in detail with reference to the attached drawings. However, the technical concept of the present application is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed content is thorough and complete and to ensure that the concept of the present application is sufficiently conveyed to those skilled in the art.

[0063] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the films and regions are exaggerated for the effective illustration of the technical content.

[0064] Additionally, although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. Accordingly, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. Furthermore, in this specification, "and / or" is used to mean including at least one of the components listed before and after it.

[0065] In the specification, singular expressions include plural expressions unless the context clearly indicates otherwise. Furthermore, terms such as "include" or "have" are intended to specify the existence of the features, numbers, steps, components, or combinations thereof described in the specification, and should not be understood as excluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof. Additionally, in this specification, "connection" is used to include both indirectly connecting multiple components and directly connecting them.

[0066] Furthermore, in describing the present application below, if it is determined that a detailed description of related known functions or configurations could unnecessarily obscure the essence of the application, such detailed description will be omitted.

[0068] FIG. 1 is a drawing for explaining a method for manufacturing an ion storage layer for an electrochromic device according to an embodiment of the present application, FIG. 2 is a drawing for explaining a method for modifying a substrate surface according to an embodiment of the present application, FIG. 3 is a drawing for explaining a method for forming a conductive layer according to an embodiment of the present application, FIG. 4 is a drawing for explaining a substrate and a conductive layer according to an embodiment of the present application, FIG. 5 is a drawing for explaining a method for forming an ion storage thin film according to an embodiment of the present application, FIG. 6 is a drawing for explaining a lattice of an ion storage material according to an embodiment of the present application, FIG. 7 is a drawing for explaining the growth direction of an ion storage material according to an embodiment of the present application, FIG. 8 is a drawing for explaining a lattice of an ion storage material doped with an auxiliary material according to an embodiment of the present application, FIG. 9 is a drawing for explaining a changed growth direction of an ion storage material according to an embodiment of the present application, and FIG. 10 is a drawing for explaining an ion storage layer for an electrochromic device according to an embodiment of the present application.

[0069] Referring to FIGS. 1 and 2, the substrate (10) can be surface modified through ion beam treatment (S110).

[0070] According to one embodiment, the substrate (10) may have flexibility and transparency. Specifically, for example, the substrate (10) may be at least one selected from the group comprising polyethylene terephthalate (PET), polyimide (PI), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), and polydimethylsiloxane (PDMS). Preferably, it may be polyethylene terephthalate (PET). However, it is not limited thereto.

[0071] According to one embodiment, by surface modification of the substrate (10), the bonding strength between the surface-modified substrate (10) and the conductive layer (20) formed on the substrate (10) in a process described later can be strengthened. Furthermore, on the surface-modified substrate (10), the growth of the conductive layer (20) and the ion storage thin film (30) formed in a process described later can be promoted. Specifically, for example, the substrate (10) has an ion beam power of 10 W or more to 100 W or less, an oxygen (O2) gas flow rate of 10 sccm or more to 30 sccm or less, a working pressure of 1 mTorr or more to 5 mTorr or less, and 1x10 -7 Torr or more up to 1x10 -5 The above ion beam treatment can be performed for 3 minutes or more and 10 minutes or less at a base pressure of Torr or less. More specifically, for example, the substrate (10) is subjected to an ion beam power of 50 W, an oxygen (O2) gas flow rate of 20 sccm, a working pressure of 2 mTorr, and 1x10 -6 The above ion beam treatment can be performed for 5 minutes at a base pressure of Torr. However, it is not limited to this.

[0072] Referring further to FIGS. 1, FIGS. 3, and FIGS. 4, a transparent conductive layer (20) can be formed on the substrate (10) (S120).

[0073] According to one embodiment, the conductive layer (20) may have conductivity, flexibility, and transparency. Specifically, for example, the conductive layer (20) may be at least one selected from the group comprising indium gallium titanium oxide (IGTO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), indium tin oxide (ITO), and fluorine-doped tin oxide (FTO). Preferably, it may be indium gallium tin oxide (IGTO). However, it is not limited thereto.

[0074] According to one embodiment, in forming the conductive layer (20), a conductive target (1) can be deposited on the substrate (10) through direct current (DC) magnetron sputtering. Specifically, for example, when the conductive layer (20) is indium gallium tin oxide (IGTO), the conductive layer (20) can be deposited by using an indium gallium tin oxide (IGTO) target doped with gallium (Ga) and titanium (Ti) in an amount of 0.1 wt% or more and 10 wt% or less, more specifically 1 wt%, as the conductive target (1) through DC magnetron sputtering. More specifically, for example, the conductive layer (20) is formed through the DC magnetron sputtering with a DC power of 10 W or more and 50 W or less, an argon (Ar) gas flow rate of 1 sccm or more and 20 sccm or less, a working pressure of 1 mTorr or more and 5 mTorr or less, and 1x10 -5Torr or more up to 1x10 -7 The conductive layer (20) can be deposited on the substrate (10) with a thickness of 150 nm or more to 250 nm or less at a base pressure of Torr or less. More specifically, for example, the conductive layer (20) can be formed through DC magnetron sputtering using a DC power of 30 W, an argon (Ar) gas flow rate of 10 sccm, a working pressure of 1 mTorr, and 1x10 -6 It can be deposited on the substrate (10) with a thickness of 200 nm at a base pressure of Torr. However, it is not limited thereto.

[0075] Referring further to FIGS. 1, 5 to 10, an ion storage material (31) that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material (32) that assists electrochromism by providing additional charge storage sites to the ion storage material (31) are simultaneously provided on the conductive layer (20), so that an ion storage thin film (30) in which the auxiliary material (32) is doped into the ion storage material (31) can be formed (S130).

[0076] According to one embodiment, in the formation of the ion storage thin film (30), the doping concentration of the auxiliary material (32) can be controlled through radio frequency (RF) magnetron sputtering. More specifically, through the radio frequency (RF) magnetron sputtering, the auxiliary target (3) containing the auxiliary material (32) can be provided with a target power greater than 50 W and less than 100 W simultaneously with the ion storage target (2) containing the ion storage material (31). More specifically, for example, through the radio frequency (RF) magnetron sputtering, the auxiliary target (3) can be provided with a target power of 80 W simultaneously with the ion storage target (2). At this time, the ion storage target (2) can be provided with a target power greater than 150 W and less than 250 W simultaneously with the auxiliary target (3) through RF magnetron sputtering, by being organically combined with the auxiliary target (3). More specifically, for example, the ion storage target (2) can be provided with a target power of 200 W simultaneously with the auxiliary target (3) through RF magnetron sputtering. For example, the ion storage target (2) may be at least one selected from the group including nickel oxide (NiO), and the auxiliary target (3) may be at least one selected from the group including molybdenum oxide (MoO3). However, it is not limited thereto.

[0077] As a result, the transmittance modulation of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, and the response speed is increased, thereby improving the electrochromic performance of the ion storage layer (100) for an electrochromic device.

[0078] In addition, the charge storage capacity of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, and the electrolyte ion, for example, lithium ion (Li + The diffusion coefficient of ) is increased, so that the electrochemical performance of the ion storage layer (100) for the electrochromic device can be improved.

[0079] In addition, a microstructure and porous structure favorable for ion diffusion are formed in the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30), and by doping with the auxiliary material (32), the crystal grain size of the ion storage material (31) is reduced and the lattice is shrunk, thereby improving the structural stability of the ion storage layer (100) for an electrochromic device.

[0080] In addition, the flexibility of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, and the mechanical durability of the ion storage layer (100) for an electrochromic device can be improved.

[0081] In addition, the long-term stability of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, and the lifespan of the ion storage layer (100) for an electrochromic device can be extended.

[0082] In addition, the electronic conductivity of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, thereby increasing the reaction speed of the ion storage layer (100) for an electrochromic device and improving the transmittance and modulation rate.

[0083] According to one embodiment, in the formation of the ion storage thin film (30), the thickness of the ion storage thin film (30) formed can be controlled through the high-frequency magnetron sputtering. More specifically, through the high-frequency magnetron sputtering, the ion storage thin film (30) can be formed with a thickness of more than 150 nm and less than 250 nm. Even more specifically, through the high-frequency magnetron sputtering, the ion storage thin film (30) can be formed with a thickness of 220 nm.

[0084] As a result, the charge storage capacity of the ion storage layer (100) for an electrochromic device manufactured from the ion storage thin film (30) is increased, and the electrochemical performance of the ion storage layer (100) for an electrochromic device can be improved.

[0085] According to one embodiment, the ion storage thin film (30) is formed through the RF magnetron sputtering with an argon (Ar) and oxygen (O2) gas flow rate ratio of 40:10 sccm or more to 49:1 sccm or less, a working pressure of 1 mTorr or more to 20 mTorr or less, and 1x10 -5 Torr or more up to 1x10 -7 The conductive layer (20) may be deposited on the conductive layer (20) at a base pressure of Torr or less. More specifically, for example, the ion storage thin film (30) may be deposited via RF magnetron sputtering at an argon (Ar) and oxygen (O2) gas flow rate ratio of 47:3 sccm, a working pressure of 10 mTorr, and 1x10 -6It can be deposited on the conductive layer (20) with a base pressure of Torr. However, it is not limited thereto.

[0086] Accordingly, the auxiliary material (32) is ion-substituted and doped into the lattice of the ion storage material (31) shown in FIG. 6, and the ion storage thin film (30) including the lattice shown in FIG. 8 can be formed. For example, when the ion storage target (2) is nickel oxide (NiO) and the auxiliary target (3) is molybdenum oxide (MoO3), the ion storage material (31) is nickel oxide (NiO), the auxiliary material (32) is molybdenum (Mo), and the ion storage thin film (30) may be molybdenum-doped nickel oxide (Mo-doped NiO, MNO). However, it is not limited thereto.

[0087] According to one embodiment, when the ion storage thin film (30) is molybdenum-doped nickel oxide (MNO), the ion storage material (31) is nickel oxide (NiO), and the auxiliary material (32) is molybdenum (Mo), the ion storage thin film (30) is nickel ions, i.e., Ni 3+ and Ni 2+ The electrochromic properties of the electrochromic device can be contributed through oxidation and reduction reactions of, more specifically, in the ion storage thin film (30), through the auxiliary material (32) doped into the ion storage material (31), Mo 6+ Ions can be introduced.

[0088] As a result, Ni in the ion storage thin film (30) 3+ It can be increased.

[0089] Accordingly, the electron density of the ion storage thin film (30) can be increased and the electrical conductivity can be improved.

[0090] As a result, the electrochromic performance of the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) can be excellent.

[0091] According to an embodiment of the present application, by doping with the auxiliary material (32), the crystal grain size of the ion storage material (31) may be reduced and the growth direction of the ion storage material (31) may be changed. More specifically, referring to FIG. 7, the ion storage material (31) may have a tendency to grow in the (111) plane. Referring to FIG. 8, the auxiliary material (32) may induce growth in the (200) plane.

[0092] As a result, the growth direction of the ion storage thin film (30) is changed, and the structure of the ion storage thin film (30) can be stabilized.

[0093] As a result, the transmittance modulation of the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) is high and the response speed is fast, so the electrochromic performance of the ion storage layer (100) for an electrochromic device can be excellent.

[0094] In addition, the charge storage capacity of the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) is large, and the electrolyte ion, for example, lithium ion (Li + The diffusion coefficient of ) is high, so the electrochemical performance of the ion storage layer (100) for the electrochromic device can be excellent.

[0095] In addition, the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) includes a microstructure and a porous structure that are favorable for ion diffusion, and by doping with the auxiliary material (32), the crystal grain size of the ion storage material (31) is small and the lattice is shrunk, so that the structural stability of the ion storage layer (100) for an electrochromic device can be excellent.

[0096] In addition, the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) has high flexibility, so the mechanical durability of the ion storage layer (100) for an electrochromic device can be excellent.

[0097] In addition, the long-term stability of the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) is high, so the lifespan of the ion storage layer (100) for an electrochromic device can be long.

[0098] In addition, the electron conductivity of the ion storage layer (100) for an electrochromic device including the ion storage thin film (30) is high, so the reaction speed of the ion storage layer (100) for an electrochromic device is fast, and the transmittance and modulation rate can be excellent.

[0100] According to the embodiments of the present application described above, an ion storage layer (100) for an electrochromic device may be provided, comprising, as shown in FIG. 10, a substrate (10), a transparent conductive layer (20) on the substrate (10), and an ion storage thin film (30) on the conductive layer (10).

[0101] According to an embodiment of the present application, in the ion storage layer (100) for the electrochromic device, the ion storage thin film (30) may comprise the ion storage material (31) and the auxiliary material (32) doped into the ion storage material (31). The ion storage material (31) contributes to electrochromism through oxidation and reduction reactions, and the auxiliary material (32) doped into the ion storage material (31) may assist electrochromism by providing additional charge storage sites to the ion storage material (31).

[0102] According to an embodiment of the present application, in the ion storage layer (100) for the electrochromic device, the auxiliary material (32) is doped by ion substitution in the lattice of the ion storage material (31), thereby reducing the crystal grain size of the ion storage material (31) and changing the growth direction of the ion storage material. More specifically, referring to FIG. 7, the ion storage material (31) tends to grow in the (111) plane, but referring to FIG. 8, the auxiliary material (32) can induce growth in the (200) plane.

[0103] As a result, the growth direction of the ion storage thin film (30) is changed, and the structure of the ion storage thin film (30) can be stabilized.

[0104] As a result, the transmittance modulation of the ion storage layer (100) for the electrochromic device is high and the response speed is fast, so the electrochromic performance of the ion storage layer (100) for the electrochromic device can be excellent.

[0105] In addition, the charge storage capacity of the ion storage layer (100) for the electrochromic device is large, and the electrolyte ion, for example, lithium ion (Li + The diffusion coefficient of ) is high, so the electrochemical performance of the ion storage layer (100) for the electrochromic device can be excellent.

[0106] In addition, the ion storage layer (100) for the electrochromic device includes a microstructure and a porous structure that facilitate ion diffusion, and by doping with the auxiliary material (32), the crystal grain size of the ion storage material (31) is small and the lattice is shrunk, so that the structural stability of the ion storage layer (100) for the electrochromic device can be excellent.

[0107] In addition, the flexibility of the ion storage layer (100) for the electrochromic device is high, so the mechanical durability of the ion storage layer (100) for the electrochromic device can be excellent.

[0108] In addition, the long-term stability of the ion storage layer (100) for the electrochromic device is high, so the lifespan of the ion storage layer (100) for the electrochromic device can be long.

[0109] In addition, the electron conductivity of the ion storage layer (100) for the electrochromic device is high, so the reaction speed of the ion storage layer (100) for the electrochromic device is fast, and the transmittance and modulation rate can be excellent.

[0111] Furthermore, according to an embodiment of the present application, an electrochromic element may be provided, comprising an electrochromic layer, an ion storage layer (100) comprising an ion storage material (31) that contributes to the electrochromicity of the electrochromic layer (30) through oxidation and reduction reactions, and an auxiliary material (32) that is doped into the ion storage material (31) to provide additional charge storage sites in the ion storage material (31) and assist in the electrochromicity.

[0112] According to an embodiment of the present application, the electrochromic layer comprises the substrate (10) and the transparent conductive layer (20) on the substrate (10), in the same manner as the ion storage layer (100) for the electrochromic device, and may include an electrochromic thin film on the conductive layer (20). The electrochromic thin film may be, for example, at least one selected from the group including tungsten trioxide (WO3). However, it is not limited thereto.

[0113] Additionally, the electrochromic element may further include an electrolyte for the electrochemical reaction of the electrochromic layer and the ion storage layer (100). The electrolyte is, for example, lithium ions (Li + It may include at least one selected from the group including ). However, it is not limited thereto.

[0114] Accordingly, through the application of an external voltage, lithium ions (Li + ) and electrons are moved to the electrochromic layer and the ion storage layer (100), so that the electrochromic element can be electrochromically driven.

[0115] According to an embodiment of the present application, the ion storage layer (100) contains nickel ions, i.e., Ni 3+ and Ni 2+ The electrochromic reaction can be contributed to through the oxidation and reduction reactions of the above, more specifically, in the ion storage layer (100), through the auxiliary material (32) doped into the ion storage material (31) Mo6+ Ions can be introduced.

[0116] As a result, Ni in the ion storage layer (100) 3+ It can be increased.

[0117] Accordingly, the electron density of the ion storage layer (100) can be increased and the electrical conductivity can be improved.

[0118] As a result, the electrochromic performance of the electrochromic device including the ion storage layer (100) can be excellent.

[0120] Specific experimental examples and characteristic evaluation results according to the embodiments of the present application are described below.

[0122] FIG. 11 is a drawing for explaining ion beam treatment according to an experimental example of the present application, and FIG. 12 is a drawing for explaining radio frequency (RF) magnetron sputtering according to an experimental example of the present application.

[0124] Preparation of an ion storage layer (ex1-1) for an electrochromic device according to Experimental Example 1-1

[0125] As illustrated in FIG. 11, polyethylene terephthalate (PET) as the substrate (10), ion beam power of 50 W, oxygen (O2) gas flow rate of 20 sccm, working pressure of 2 mTorr, and 1x10 -6 The surface was modified by the above ion beam treatment for 5 minutes at a base pressure of Torr (see Table 1).

[0126] Through DC magnetron sputtering, an indium gallium tin oxide (IGTO) target doped with 1 wt% each of gallium (Ga) and titanium (Ti) is used as the conductive target (1) at a DC power of 30 W, an argon (Ar) gas flow rate of 10 sccm, a working pressure of 1 mTorr, and 1x10 -6 The conductive layer (20) was formed by depositing a thickness of 200 nm on the substrate (10) with a base pressure of Torr (see Table 2).

[0127] As illustrated in FIG. 12, nickel oxide (NiO) is simultaneously supplied to the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) to the auxiliary target (3) with a target power of 50 W via RF magnetron sputtering, with an argon (Ar) and oxygen (O2) gas flow rate ratio of 47:3 sccm, a working pressure of 10 mTorr, and 1x10 -6 An ion storage thin film (30) was formed by depositing it on the conductive layer (20) with a thickness of 220 nm at a base pressure of Torr (see Table 3), thereby manufacturing an ion storage layer (ex1-1) for an electrochromic device according to Experimental Example 1-1.

[0129] Preparation of an ion storage layer (ex1-2) for an electrochromic device according to Experimental Example 1-2

[0130] In the above-described experimental example 1-1, nickel oxide (NiO) was simultaneously provided as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was provided as the auxiliary target (3) with a target power of 80 W, thereby manufacturing an ion storage layer (ex1-2) for an electrochromic device according to experimental example 1-2.

[0132] Preparation of an ion storage layer (ex1-3) for an electrochromic device according to Experimental Example 1-3

[0133] In the above-described experimental example 1-1, nickel oxide (NiO) was simultaneously provided as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was provided as the auxiliary target (3) with a target power of 100 W, thereby manufacturing an ion storage layer (ex1-3) for an electrochromic device according to experimental example 1-3.

[0135] Preparation of an ion storage layer (ex1-4) for an electrochromic device according to Experimental Example 1-4

[0136] In the above-described experimental example 1-1, nickel oxide (NiO) was simultaneously supplied as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was supplied as the auxiliary target (3) with a target power of 130 W, thereby manufacturing an ion storage layer (ex1-4) for an electrochromic device according to experimental example 1-4.

[0138] Preparation of an ion storage layer (ex1-5) for an electrochromic device according to Experimental Example 1-5

[0139] In the above-described experimental example 1-1, nickel oxide (NiO) was simultaneously supplied as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was supplied as the auxiliary target (3) with a target power of 150 W, thereby manufacturing an ion storage layer (ex1-5) for an electrochromic device according to experimental example 1-5.

[0141] Preparation of an ion storage layer (ex1-6) for an electrochromic device according to Experimental Example 1-6

[0142] In the above-described experimental example 1-1, nickel oxide (NiO) was simultaneously supplied as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was supplied as the auxiliary target (3) with a target power of 180 W, thereby manufacturing an ion storage layer (ex1-6) for an electrochromic device according to experimental example 1-6.

[0144] Preparation of an ion storage layer (ex1-7) for an electrochromic device according to Experimental Example 1-7

[0145] In the above-described Experimental Example 1-1, nickel oxide (NiO) was simultaneously provided as the ion storage target (2) with a target power of 200 W and molybdenum oxide (MoO3) was provided as the auxiliary target (3) with a target power of 200 W, thereby manufacturing an ion storage layer (ex1-7) for an electrochromic device according to Experimental Example 1-7.

[0147] Experimental Examples 1-1 to 1-7 described above can be summarized as shown in Tables 1 to 3 below.

[0148] division Base pressure (Torr) Ion beam power (W) O2 gas flow rate (sccm) Working pressure (mTorr) Processing time (min) Experimental Examples 1-1 to 1-7 (ex1-1 to ex1-7) 1×10 -6 50 20 2 5

[0150] division Base pressure (Torr) DC Power (W) Ar gas flow rate (sccm) Working pressure (mTorr) Thickness (nm) Experimental Examples 1-1 to 1-7 (ex1-1 to ex1-7) 1×10 -6 30 10 1 200

[0152] division NiO RF power (W) MoO3RF Power (W) Ar:O2 gas flow rate (sccm) Working pressure (mTorr) Thickness (nm) Experiment Example 1-1 (ex1-1) 200 50 47:3 10 220 Experiment Example 1-2 (ex1-2) 200 80 47:3 10 220 Experiment Example 1-3 (ex1-3) 200 100 47:3 10 220 Experimental Example 1-4 (ex1-4) 200 130 47:3 10 220 Experimental Example 1-5 (ex1-5) 200 150 47:3 10 220 Experimental Example 1-6 (ex1-6) 200 180 47:3 10 220 Experiment Example 1-7 (ex1-7) 200 200 47:3 10 220

[0154] FIG. 13 is the cyclic voltammetry (CV) measurement result of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application.

[0155] Referring to FIG. 13, in a cyclic voltammetry (CV) performed at a scan rate of 100 mV / s within a voltage range of -0.8 V to 1.3 V, according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), it can be seen that as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases, the area under the curve of the cyclic voltammetry (CV) becomes wider. According to Experimental Example 1-2 (ex1-2), when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W, it can be seen that the area under the curve of the cyclic voltammetry (CV) is widest. On the other hand, it can be seen that as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Examples 1-3 to 1-7 (ex1-3 to ex1-7) which exceed the boundary of Experimental Example 1-2 (ex1-2), the area under the curve of the cyclic voltammetry (CV) actually decreases.

[0156] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, critical significance can be demonstrated and excellent electrochemical performance can be demonstrated.

[0158] division MoO3RF Power (W) Cathode peak diffusion coefficient (cm²) 2 / s) Anodic peak diffusion coefficient (cm²) 2 / s) Experiment Example 1-1 (ex1-1) 50 1.36ⅹ10 -8 1.37ⅹ10 -8 Experiment Example 1-2 (ex1-2) 80 1.67ⅹ10 -8 1.28ⅹ10 -8 Experiment Example 1-3 (ex1-3) 100 0.57ⅹ10 -8 0.75ⅹ10 -8

[0160] Table 4 shows the calculation results of the anodic peak diffusion coefficient and cathodic peak diffusion coefficient of the ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-3 of the present application.

[0161] Table 4 shows the results calculated according to Equation 1 below, after measuring the cyclic voltammetry (CV) of the ion storage layers (ex1-1 to ex1-3) for electrochromic devices according to Experimental Examples 1-1 to 1-3 above at different scan speeds.

[0162] <Equation 1>

[0163] D 0.5 =i p / (k×n 1.5 ×A×C×v 0.5 )

[0164] (here, i p ε is the peak current (A), and k is Cmol -1 V -1 / 2 2.69 x 10 units 5 Constant, n is the number of electrons, A is the electrode area (cm²) 2 ), C is the active ion concentration (mol / cm²) 3 ), D is the effective diffusion coefficient (cm²) 2 / s), and v is 10~100 mVs -1 Injection rate (V / s) in the range

[0165] Referring to Table 4, it can be seen that according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), the cathode peak diffusion coefficient increases as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases. According to Experimental Example 1-2 (ex1-2), it can be seen that the cathode peak diffusion coefficient is greatest when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W. On the other hand, with Experimental Example 1-2 (ex1-2) as the boundary, it can be seen that when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Example 1-3 (ex1-3) which exceeds this value, the cathode peak diffusion coefficient actually decreases.

[0166] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, critical significance can be demonstrated and excellent electrochemical performance can be demonstrated.

[0168] FIG. 14 is the chronoaperometry (CA) measurement result of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application.

[0169] Referring to FIG. 14, chronoamperometry (CA) was measured by applying voltage for 30 seconds during coloring and decolorization, respectively, within a voltage range of -0.8 V to 1.3 V. The measurement results can be summarized as shown in Table 5 below.

[0170] division MoO3RF Power (W) Decolorization transmittance (%) Color transmittance (%) Transmittance Modulation (%) Decolorization reaction time(s) Coloring reaction time(s) NiO 0 70.85 37.07 33.78 6.57 9.03 Experiment Example 1-1 (ex1-1) 50 64.26 30.87 33.39 10.12 12.86 Experiment Example 1-2 (ex1-2) 80 63.96 29.68 34.29 3.28 5.75 Experiment Example 1-3 (ex1-3) 100 55.08 28.7 26.37 5.74 8.21 Experimental Example 1-4 (ex1-4) 130 61.36 41.42 19.94 10.94 18.47 Experimental Example 1-5 (ex1-5) 150 69.25 56.34 12.91 3.45 16.96 Experimental Example 1-6 (ex1-6) 180 74.94 68.96 5.98 9.85 21.2 Experiment Example 1-7 (ex1-7) 200 78.51 77.7 0.81 16.83 25.72

[0172] Referring to FIG. 14 and Table 5, it can be seen that according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases, the transmittance modulation increases. According to Experimental Example 1-2 (ex1-2), it can be seen that the transmittance modulation is greatest when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W. On the other hand, with Experimental Example 1-2 (ex1-2) as the boundary, it can be seen that as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Examples 1-3 to 1-7 (ex1-3 to ex1-7) exceeding this value, the transmittance modulation actually decreases.

[0173] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, critical significance can be demonstrated and excellent electrochromic performance can be demonstrated.

[0174] Additionally, referring to FIG. 14 and Table 5, it can be seen that according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases, the decolorization reaction time decreases. According to Experimental Example 1-2 (ex1-2), it can be seen that the decolorization reaction time is shortest when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W. On the other hand, with Experimental Example 1-2 (ex1-2) as the boundary, it can be seen that as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Examples 1-3 to 1-7 (ex1-3 to ex1-7) which exceed this value, the decolorization reaction time actually increases.

[0175] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, critical significance can be demonstrated and excellent electrochromic performance can be demonstrated.

[0176] Additionally, referring to FIG. 14 and Table 5, it can be seen that according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases, the coloring reaction time decreases. According to Experimental Example 1-2 (ex1-2), it can be seen that the coloring reaction time is shortest when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W. On the other hand, with Experimental Example 1-2 (ex1-2) as the boundary, it can be seen that as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Examples 1-3 to 1-7 (ex1-3 to ex1-7) which exceed this value, the coloring reaction time actually increases.

[0177] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, critical significance can be demonstrated and excellent electrochromic performance can be demonstrated.

[0179] FIG. 15 is the result of measuring the transmittance in the visible light region of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application, and FIG. 16 is the result of measuring the chronoamperometric (CA) of an ion storage layer for an electrochromic device according to Experimental Examples 1-1 to 1-7 of the present application.

[0180] Referring to FIG. 15, it can be seen that the ion storage layer (ex1-2) for the electrochromic device according to Experimental Example 1-2 initially exhibits stronger light absorption in the visible light region and darker coloration due to Mo doping. Additionally, it can be seen that the ion storage layer (ex1-2) for the electrochromic device according to Experimental Example 1-2 initially had a somewhat slow response speed during the initial cycle, but gradually stabilized as the operation was repeated, ultimately exhibiting improved optical performance.

[0181] Referring to FIG. 16, when chronoamperometric (CA) was measured by applying voltage for 30 seconds each during coloring and decolorization within a voltage range of -0.8 V to 1.3 V, it can be confirmed that the current flow of the ion storage layer (ex1-1 to ex1-7) for the electrochromic device according to Experimental Examples 1-1 to 1-7 is stably maintained.

[0183] FIG. 17 is a field emission scanning electron microscope (FESEM) image of an ion storage thin film in an ion storage layer for an electrochromic device formed of nickel oxide (NiO) and experimental examples 1-1 to 1-7 of the present application, and FIG. 18 is a cross-sectional field emission scanning electron microscope (FESEM) image of an ion storage thin film in an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to experimental example 1-2 of the present application.

[0184] Referring to FIG. 17, a typical columnar structure can be observed in the case of an ion storage thin film formed of nickel oxide (NiO). On the other hand, in the ion storage thin films according to Experimental Examples 1-1 to 1-7 (ex1-1 to ex1-7) of the present application, a highly porous amorphous structure containing subgrains similar to garlic flowers can be observed.

[0185] In particular, when the target power for providing molybdenum oxide (MoO3) as the auxiliary target (3) according to the above experimental example 1-2 (ex1-2) is 80 W, a uniform particle distribution and a stable porous structure can be confirmed in the ion storage thin film.

[0186] Thus, optimal Mo doping can be demonstrated when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W.

[0187] Referring to Fig. 18, unlike the ion storage thin film formed of nickel oxide (NiO), the ion storage thin film according to Experimental Example 1-2 (ex1-2) shows distinct changes in the crystal growth direction and interface. This implies that a sophisticated polycrystalline structure is formed because Mo doping influences the grain growth and nucleation processes, and this can be seen as an important factor contributing to the improvement of the electrochemical reactivity and optical performance of the ion storage thin film according to Experimental Example 1-2 (ex1-2).

[0189] FIG. 19 is an X-ray diffraction (XRD) graph of an ion storage thin film in an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application, and FIG. 20 is an X-ray diffraction (XRD) graph of an ion storage thin film in an ion storage layer for an electrochromic device according to Experimental Example 1-1 and Experimental Examples 1-3 to 1-7 of the present application.

[0190] The X-ray diffraction (XRD) measurement results of the ion storage thin film (ex1-2) according to the above experimental example 1-2 shown in Fig. 19 can be summarized as shown in Table 6 below.

[0191] No. 2-theta d Heightt FWHM Size deg Å counts deg Å 1 37.18 2.4183 1273 0.65 130 2 43.32 2.0887 5064 0.553 155 3 62.92 1.4772 2075 0.808 115 4 75.52 1.259 309 1 100 5 79.58 1.2046 287 0.78 133

[0193] In addition, the X-ray diffraction (XRD) measurement results of the ion storage thin film formed from the nickel oxide (NiO) shown in Fig. 19 can be summarized as shown in Table 7 below.

[0194] No. 2-theta d Heightt FWHM Size deg Å counts deg Å 1 37.02 2.4284 9686 0.436 192.2 2 43.00 2.103 383 1.19 72 3 62.58 1.48436 883 0.59 157.5 4 75.04 1.2658 1218 0.732 137 5 78.92 1.213 119 0.98 105

[0196] Referring to Fig. 19, the ion storage thin film formed from the nickel oxide (NiO) exhibits an FCC structure, and the strongest diffraction peak can be observed at the (111) plane. On the other hand, in the case of the ion storage thin film according to Experimental Example 1-2 (ex1-2), it can be observed that the main peak tends to shift toward the higher 2θ direction without any new diffraction peaks. This is because, according to Bragg's law, Mo 6+ This may be because the lattice has shrunk due to ion exchange.

[0197] Referring to Tables 6 and 7, it can be seen that the grain size of the ion storage film according to Experimental Example 1-2 (ex1-2) is reduced compared to the ion storage film formed with nickel oxide (NiO). Additionally, in the ion storage film according to Experimental Example 1-2 (ex1-2), the growth of the (200) plane, which is a different crystal plane from the ion storage film formed with nickel oxide (NiO), can be observed.

[0198] As a result, in the above experimental example 1-2 (ex1-2), it can be proven that the crystal growth direction was changed through Mo doping.

[0199] Referring to FIG. 20, unlike the above experimental example 1-2 (ex1-2), in the X-ray diffraction (XRD) of experimental example 1-1 and experimental examples 1-3 to 1-7 (ex1-1, ex1-3 to ex1-7), it can be seen that the intensity of the diffraction peaks is generally weak and the dispersion of the peaks is prominent.

[0200] Thus, excellent stability can be demonstrated when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W.

[0202] FIG. 21 is the result of X-ray photoelectron spectroscopy (XPS) nickel (Ni) peak analysis of an ion storage thin film formed of an ion storage layer for an electrochromic device and an ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application, FIG. 22 is the result of X-ray photoelectron spectroscopy (XPS) molybdenum (Mo) peak analysis of an ion storage thin film for an electrochromic device in an ion storage layer according to Experimental Example 1-2 of the present application, and FIG. 23 is the result of energy dispersive spectroscopy (EDS) analysis of an ion storage thin film for an electrochromic device in an ion storage layer according to Experimental Example 1-2 of the present application.

[0203] Figures 21 and 22 can be summarized as shown in Table 8 below.

[0204] Peak Pristine NiO MNO BE (eV) Ni 2+ 2p 3 / 2 853.49 854.05 Ni 3+ 2p 3 / 2 855.24 855.62 Ni 2+ 2p 3 / 2 shake-up satellite 860.66 861.27 Ni 3+ 2p 3 / 2 shake-up satellite 864.59 866.28 Ni2+2p 1 / 2 870.91 871.81 Ni3+2p 1 / 2 872.62 873.49 Ni 2+ 2p 1 / 2 shake-up satellite 878.24 879.54 Ni 3+ 2p 1 / 2 shake-up satellite 880.57 883.82

[0206] In addition, Fig. 23 can be summarized as shown in Table 9 below.

[0207] Formula Mass (%) Atom(%) Sigma K ratio Line O 24.84 56.27 0.04 0.1402310 K Ni 63.97 39.50 0.17 0.6616423 K Mo 11.19 4.23 0.08 0.0795258 L Total 100 100 - - -

[0209] In addition, the results of the energy dispersive spectroscopy (EDS) analysis of the ion storage thin film in the ion storage layer for the electrochromic device according to Experimental Examples 1-1 to 1-3 above can be summarized as shown in Table 10 below.

[0210] division MoO3RF Power (W) Ni[%] Mo[%] O[%] Experiment Example 1-1 (ex1-1) 50 40.96 2.02 57.02 Experiment Example 1-2 (ex1-2) 80 39.50 4.23 56.27 Experiment Example 1-3 (ex1-3) 100 34.64 5.72 59.64

[0212] Referring to FIG. 21 and Table 8, Ni in the ion storage thin film (ex1-2) according to Experimental Example 1-2 is higher than in the ion storage thin film formed of the nickel oxide (NiO). 3+ It can be confirmed that the ratio has increased.

[0213] This demonstrates that, in the above Experimental Example 1-2 (ex1-2), additional electron acceptance in NiO was promoted by Mo doping, and it can be confirmed that the binding energy spectrum of the Ni component shows a tendency to shift to the right. In the above Experimental Example 1-2 (ex1-2), high Ni 3+ The ratio is a result consistent with the fact that the ion storage thin film (ex1-2) according to Experimental Example 1-2 above exhibits a darker initial color than the ion storage thin film formed of nickel oxide (NiO). Ni in the ion storage thin film (ex1-2) according to Experimental Example 1-2 above 3+ Although a high content of may reduce the reaction rate by decreasing initial ionic conductivity, as the oxidation / reduction reaction proceeds, Ni 3+ is stably Ni 2+ It can transition to a state.

[0214] Referring to FIG. 22, in the ion storage thin film (ex1-2) according to Experimental Example 1-2 above, Mo 6+ The existence of Ni 2+ It contributes to maintaining the structural stability of the ion storage thin film (ex1-2) according to Experimental Example 1-2 above, which can increase the transmittance and reaction rate of the ion storage thin film.

[0215] Referring to Figure 23 and Table 9, in the ion storage thin film (ex1-2) according to Experimental Example 1-2, the atomic ratios of Mo, Ni, and O were measured to be 4.23%, 39.50%, and 56.27%, respectively, and it can be confirmed that they were uniformly deposited.

[0216] Thus, it can be proven that Mo was successfully doped into the NiO lattice in the ion storage thin film (ex1-2) according to Experimental Example 1-2 above. Furthermore, it can be proven that Mo doping is a major factor contributing to the improvement of the electrochemical performance of the MNO thin film.

[0217] Referring to Table 10, it can be seen that according to Experimental Example 1-1 and Experimental Example 1-2 (ex1-1 to ex1-2), as the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases, the atomic ratio of O decreases. According to Experimental Example 1-2 (ex1-2), when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) is 80 W, it can be seen that the atomic ratio of O is the smallest. On the other hand, with Experimental Example 1-2 (ex1-2) as the boundary, when the target power providing molybdenum oxide (MoO3) to the auxiliary target (3) increases according to Experimental Example 1-3 (ex1-3) which exceeds this, it can be seen that the atomic ratio of O actually increases.

[0218] Thus, critical significance can be demonstrated when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W.

[0220] FIG. 24 is the cyclic voltammetry (CV) measurement result of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application, FIG. 25 is the electrochemical impedance spectroscopy (EIS) measurement result of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application, FIG. 26 is the long-term stability (a) transmittance and (b) current density measurement result of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed of nickel oxide (NiO) according to Experimental Example 1-2 of the present application.

[0221] The cyclic voltammetry (CV) measured through Fig. 24 can be calculated as shown in Table 11 below.

[0222] division MoO3RF Power (W) Cathode peak diffusion coefficient (cm²) 2 / s) Anodic peak diffusion coefficient (cm²) 2 / s) NiO 0 1.61×10- 8 1.12×10- 8 Experiment Example 1-2 (ex1-2) 80 1.65×10- 8 1.27×10- 8

[0224] Referring to FIG. 24, Table 11, and FIG. 25, it can be seen that the ion storage layer (ex1-2) for the electrochromic device according to Experimental Example 1-2 has improved ion diffusion kinetics due to Mo doping.

[0225] In addition, referring to FIG. 26, through a long-term stability measurement of 30,000 s, it can be confirmed that the ion storage layer for an electrochromic device according to Experimental Example 1-2 (ex1-2) has superior long-term stability compared to the ion storage layer for an electrochromic device formed of nickel oxide (NiO).

[0226] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, excellent long-term stability and lifespan can be demonstrated.

[0228] FIG. 27 shows the bending critical limit and fatigue repetition test results of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed with nickel oxide (NiO) according to Experimental Example 1-2 of the present application, FIG. 28 shows a field emission scanning electron microscope (FESEM) image after the fatigue repetition test of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed with nickel oxide (NiO) according to Experimental Example 1-2 of the present application, FIG. 29 shows the long-term stability (a) transmittance and (b) current density measurement results after the fatigue repetition test of the ion storage layer for an electrochromic device and the ion storage layer for an electrochromic device formed with nickel oxide (NiO) according to Experimental Example 1-2 of the present application.

[0229] Referring to FIG. 27, it can be seen that the ion storage layer for an electrochromic device formed of nickel oxide (NiO) has an internal bending characteristic of 5 mm and an external bending characteristic of 12 mm. On the other hand, the ion storage layer for an electrochromic device according to Experimental Example 1-2 (ex1-2) has an internal bending characteristic of 3 mm and an external bending characteristic of 10 mm, which can be seen as having higher flexibility than the ion storage layer for an electrochromic device formed of nickel oxide (NiO).

[0230] In addition, referring to FIG. 27, as a result of conducting a fatigue bending test over 10,000 cycles at a critical radius, it can be confirmed that both the ion storage layer for the electrochromic device according to Experimental Example 1-2 (ex1-2) and the ion storage layer for the electrochromic device formed from nickel oxide (NiO) maintain stable performance even under repetitive mechanical stress, and there is no significant change in electrical resistance.

[0231] Thus, excellent mechanical durability can be demonstrated when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W.

[0232] Referring to Fig. 28, the structural integrity of the ion storage layer for an electrochromic device (ex1-2) according to Experimental Example 1-2 and the ion storage layer for an electrochromic device formed of nickel oxide (NiO) was evaluated before and after bending using a field emission scanning electron microscope (FESEM), and it was confirmed that there were almost no surface cracks or defects after the bending test.

[0233] Thus, excellent mechanical durability can be demonstrated when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W.

[0234] Referring to FIG. 29, in the case of the ion storage layer for an electrochromic device formed of nickel oxide (NiO), it can be seen that it exhibited stable operation only during the initial few cycles in a long-term cycling test to evaluate long-term operational stability after a bending test, and subsequently deteriorated rapidly. On the other hand, it can be seen that the ion storage layer for an electrochromic device according to Experimental Example 1-2 (ex1-2) maintained more stable operation than the ion storage layer for an electrochromic device formed of nickel oxide (NiO).

[0235] Thus, when molybdenum oxide (MoO3) is provided as the auxiliary target (3) with a target power of 80 W, excellent mechanical durability, excellent long-term stability, and lifespan can be demonstrated.

[0237] Preparation of an ion storage layer (ex2-1) for an electrochromic device according to Experimental Example 2-1

[0238] An ion storage layer (ex2-1) for an electrochromic device according to Experimental Example 2-1 was prepared by providing an argon (Ar) and oxygen (O2) gas flow rate ratio of 47:3 sccm, identical to Experimental Example 1-2 described above.

[0240] Preparation of an ion storage layer (ex2-2) for an electrochromic device according to Experimental Example 2-2

[0241] In the above-described Experimental Example 2-1, an ion storage layer (ex2-2) for an electrochromic device according to Experimental Example 2-2 was prepared by providing an argon (Ar) and oxygen (O2) gas flow rate ratio of 45:5 sccm.

[0243] Preparation of an ion storage layer (ex2-3) for an electrochromic device according to Experimental Example 2-3

[0244] In the above-described Experimental Example 2-1, an ion storage layer (ex2-3) for an electrochromic device according to Experimental Example 2-3 was prepared by providing an argon (Ar) and oxygen (O2) gas flow rate ratio of 40:10 sccm.

[0246] Experimental Examples 2-1 to 2-3 described above can be summarized as shown in Table 12 below.

[0247] division Ar:O2 gas flow rate (sccm) Experiment Example 2-1 (ex2-1) 47:3 Experiment Example 2-2 (ex2-2) 45:5 Experiment Example 2-3 (ex2-3) 40:10

[0249] FIG. 30 shows the (a) cyclic voltammetry (CV) and (b) transmittance modulation measurements according to the oxygen partial pressure ratio at 550 nm of an ion storage layer for an electrochromic device according to Experimental Examples 2-1 to 2-3 of the present application.

[0250] Referring to Fig. 30, it can be seen that the area under the curve of the cyclic voltammetry (CV) is widest when the argon (Ar) and oxygen (O2) gas flow rates are provided at a ratio of 47:3 sccm according to the above experimental example 2-1 (ex2-1).

[0251] Thus, excellent electrochemical performance can be demonstrated when argon (Ar) and oxygen (O2) gases are provided to the auxiliary target (3) at a flow rate ratio of 47:3 sccm.

[0253] Preparation of an ion storage layer (ex3-1) for an electrochromic device according to Experimental Example 3-1

[0254] In the above-described experimental example 1-2, the ion storage thin film (30) was deposited on the conductive layer (20) with a thickness of 150 nm to produce an ion storage layer (ex3-1) for an electrochromic device according to experimental example 3-1.

[0256] Preparation of an ion storage layer (ex3-2) for an electrochromic device according to Experimental Example 3-2

[0257] In the same manner as in Experimental Example 1-2 described above, the ion storage thin film (30) was deposited on the conductive layer (20) to a thickness of 150 nm to produce an ion storage layer (ex3-2) for an electrochromic device according to Experimental Example 3-2.

[0259] Preparation of an ion storage layer (ex3-3) for an electrochromic device according to Experimental Example 3-3

[0260] In the above-described experimental example 3-1, the ion storage thin film (30) was deposited on the conductive layer (20) with a thickness of 250 nm to produce an ion storage layer (ex3-3) for an electrochromic device according to experimental example 3-3.

[0262] Experimental Examples 3-1 to 3-3 described above can be summarized as shown in Table 13 below.

[0263] division Thickness (nm) Experiment Example 3-1 (ex3-1) 150 Experiment Example 3-2 (ex3-2) 220 Experiment Example 3-3 (ex3-3) 250

[0265] FIG. 31 shows the (a) cyclic voltammetry (CV) and (b) transmittance modulation measurements according to the oxygen partial pressure ratio at 550 nm of an ion storage layer for an electrochromic device according to Experimental Examples 3-1 to 3-3 of the present application.

[0266] Referring to FIG. 30, it can be seen that according to Experimental Example 3-1 and Experimental Example 3-2 (ex3-1 to ex3-2), as the thickness of the ion storage thin film (30) deposited on the conductive layer (20) increases, the curve area of ​​the cyclic voltammetry (CV) becomes wider. According to Experimental Example 3-2 (ex3-2), when the thickness of the ion storage thin film (30) deposited on the conductive layer (20) is 220 nm, it can be seen that the curve area of ​​the cyclic voltammetry (CV) is widest. On the other hand, with Experimental Example 3-2 (ex3-2) as the boundary, if the thickness of the ion storage thin film (30) deposited on the conductive layer (20) increases further according to Experimental Example 3-3 (ex3-3) which exceeds this, it can be seen that the curve area of ​​the cyclic voltammetry (CV) becomes smaller.

[0267] Thus, when the ion storage thin film (30) is deposited on the conductive layer (20) with a thickness of 220 nm, critical significance can be demonstrated and excellent electrochemical performance can be demonstrated.

[0269] Although the present application has been described in detail using preferred embodiments, the scope of the present application is not limited to specific embodiments and should be interpreted by the appended claims. Furthermore, those skilled in the art will understand that many modifications and variations are possible without departing from the scope of the present application. Explanation of the symbols

[0271] 1: Challenge Target 2: Ion storage target 3: Secondary Target 10: Substrate 20: Evangelism layer 30: Ion storage thin film 31: Ion storage material 32: Auxiliary substances 100: Ion storage layer

Claims

Claim 1 A method for manufacturing an ion storage layer for an electrochromic device, comprising: a step of forming a transparent conductive layer on a substrate; and a step of simultaneously providing an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material on the conductive layer, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material, wherein the auxiliary material is doped by ion substitution in the lattice of the ion storage material, and the crystal grain size of the ion storage material is reduced and the growth direction of the ion storage material is changed by doping with the auxiliary material. Claim 2 A method for manufacturing an ion storage layer for an electrochromic device according to claim 1, wherein the step of forming the ion storage thin film comprises controlling the doping concentration of the auxiliary material through magnetron sputtering, wherein in the magnetron sputtering, the auxiliary target containing the auxiliary material is provided at a target power greater than 50 W and less than 100 W simultaneously with the ion storage target containing the ion storage material. Claim 3 A method for manufacturing an ion storage layer for an electrochromic device according to claim 2, wherein, in the magnetron sputtering, the ion storage target is provided with a target power of more than 150 W and less than 250 W simultaneously with the auxiliary target. Claim 4 A method for manufacturing an ion storage layer for an electrochromic device according to claim 1, wherein the ion storage thin film is formed with a thickness of more than 150 nm and less than 250 nm. Claim 5 delete Claim 6 A method for manufacturing an ion storage layer for an electrochromic device, comprising: a step of forming a transparent conductive layer on a substrate; and a step of simultaneously providing an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material on the conductive layer, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material, wherein the ion storage material grows in a (111) plane and the auxiliary material induces growth in a (200) plane, and the structure of the ion storage thin film is stabilized by a change in the growth direction. Claim 7 A method for manufacturing an ion storage layer for an electrochromic device according to claim 2, wherein the ion storage target comprises nickel oxide (NiO), the auxiliary target comprises molybdenum oxide (MoO3), the ion storage material comprises nickel oxide (NiO), the auxiliary material comprises molybdenum (Mo), and the ion storage thin film comprises molybdenum-doped nickel oxide (Mo-doped NiO). Claim 8 In claim 7, in the ion storage thin film, Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ A method for manufacturing an ion storage layer for an electrochromic device, comprising increasing the electron density and improving electrical conductivity. Claim 9 A method for manufacturing an ion storage layer for an electrochromic device, comprising: a step of surface modifying a substrate through ion beam treatment; a step of forming a transparent conductive layer on the substrate; and a step of simultaneously providing an ion storage material that contributes to electrochromism through oxidation and reduction reactions and an auxiliary material that assists electrochromism by providing additional charge storage sites to the ion storage material on the conductive layer, thereby forming an ion storage thin film in which the auxiliary material is doped into the ion storage material, wherein the adhesion between the surface-modified substrate and the conductive layer is strengthened by the surface modification of the substrate, and the growth of the conductive layer and the ion storage thin film is promoted on the surface-modified substrate. Claim 10 An ion storage layer for an electrochromic device comprising: a substrate; a transparent conductive layer on the substrate; and an ion storage thin film on the conductive layer, wherein the ion storage thin film comprises an ion storage material and an auxiliary material doped into the ion storage material, wherein the ion storage material contributes to electrochromism through oxidation and reduction reactions, and the auxiliary material doped into the ion storage material assists in electrochromism by providing additional charge storage sites to the ion storage material. Claim 11 An ion storage layer for an electrochromic device, comprising: a substrate; a transparent conductive layer on the substrate; and an ion storage thin film on the conductive layer, wherein the ion storage thin film comprises an ion storage material and an auxiliary material doped into the ion storage material, wherein the ion storage material contributes to electrochromism through oxidation and reduction reactions, and the auxiliary material doped into the ion storage material assists the electrochromism by providing additional charge storage sites to the ion storage material, and wherein the auxiliary material is doped by ion substitution in the lattice of the ion storage material, reduces the crystal grain size of the ion storage material, and changes the growth direction of the ion storage material. Claim 12 An ion storage layer for an electrochromic device according to claim 10, wherein the ion storage material comprises nickel (Ni), the auxiliary material comprises molybdenum (Mo), and the ion storage thin film comprises molybdenum-doped nickel oxide (Mo-doped NiO). Claim 13 In claim 12, in the ion storage thin film, Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ An ion storage layer for an electrochromic device, comprising an increase in electron density and improved electrical conductivity. Claim 14 An electrochromic device comprising: an electrochromic layer; and an ion storage layer comprising an ion storage material that contributes to the electrochromicity of the electrochromic layer through oxidation and reduction reactions, and an auxiliary material that is doped into the ion storage material to provide additional charge storage sites in the ion storage material and assist the electrochromicity. Claim 15 In claim 14, the ion storage layer is Ni 3+ and Ni 2+ Contributing to the electrochromism through the oxidation and reduction reactions of, wherein Mo through the doping of the auxiliary material 6+ Ions are introduced and Ni 3+ An electrochromic device comprising an increase in electron density and improved electrical conductivity.

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