Electrochromic device

Abstract

One embodiment of the present invention provides an electrode substrate comprising: a substrate; an engraved recess which is provided in the substrate; a first anti-reflection layer which is disposed in the recess; a first electrode layer which is disposed so as to cover the first anti-reflection layer and does not deviate in position from the upper portion of the recess; a second electrode layer which has an area overlapping the first electrode layer and is disposed at the upper surface of the substrate and the side surface of the recess; and a protection layer which is disposed at the recess so as to cover at least a portion of the second electrode layer.

Description

electrochromic devices

[0001] The present invention relates to an electrochromic device.

[0002] Electrochromic materials are materials that reversibly change color depending on the direction of the electric field when voltage is applied from an external power source. These materials change color reversibly through an electrochemical redox reaction. They have the characteristic of changing color when an electrical signal is applied externally or when no electrical signal is applied, and then fading.

[0003] A typical electrochromic device includes an electrochromic (EC) electrode layer and a counter electrode (CE) layer, which are separated by an ionically conductive layer that is highly resistive to electrons and highly conductive to ions.

[0004] Electrochromic elements can be formed in various ways, but for example, a method that includes a layer formation process using adsorption has the problem of a complicated manufacturing process and increased cost, and has limitations in applying it to flexible elements because it requires a high-temperature heat treatment process.

[0005] In addition, the solution type in which the electrochromic material is dissolved in the electrolyte solution has limitations in the precise control ability and stability improvement of the device.

[0006] The present invention aims to provide a low-resistance electrode substrate with improved durability and an electrochromic device including the same.

[0007] One embodiment of the present invention provides an electrode substrate including a substrate, an engraved groove provided in the substrate, a first anti-reflection layer disposed in the groove, a first electrode layer disposed to cover the first anti-reflection layer and not extending beyond an upper portion of the groove, a second electrode layer having an area overlapping the first electrode layer and disposed on an upper surface of the substrate and a side surface of the groove, and a protective layer disposed to cover at least a portion of the second electrode layer in the groove.

[0008] The electrode substrate according to the present invention has a starburst phenomenon alleviated and a moire phenomenon improved, and by applying the electrode substrate according to an embodiment of the present invention, an electrochromic device having high reliability and durability can be obtained even after repeated driving.

[0009] FIG. 1 is a cross-sectional view schematically showing an electrode substrate according to one embodiment of the present invention.

[0010] Figure 2 schematically illustrates an electrode substrate according to another embodiment of the present invention.

[0011] Figure 3 shows the results of evaluating the moire phenomenon according to the negative pattern of the electrode substrate according to one embodiment and a comparative example of the present invention.

[0012] Figure 4 shows the results of evaluating the starburst phenomenon according to the anti-reflection layer of the electrode substrate according to one embodiment and a comparative example of the present invention.

[0013] Figures 5 to 7 show images according to the presence or absence of a protective layer on an electrode substrate according to one embodiment and a comparative example of the present invention.

[0014] Figures 8 and 9 show the results of confirming the discoloration and decolorization characteristics according to the presence or absence of a protective layer on an electrode substrate according to one embodiment and a comparative example of the present invention.

[0015] Figure 10 shows the results of evaluating the optimization of the thickness and content of the protective layer of the electrode substrate according to one embodiment and a comparative example of the present invention.

[0016] Figure 11 shows the results of evaluating reliability according to the presence or absence of a protective layer for an electrochromic device according to one embodiment and a comparative example of the present invention.

[0017] Figure 12 shows the results of evaluating the starburst phenomenon according to the type of anti-reflection layer of the electrode substrate according to one embodiment and a comparative example of the present invention.

[0018] <Explanation of symbols>

[0019] 10, 10`: Electrode substrate

[0020] 100: substrate 200: first electrode layer

[0021] 310: First anti-reflection layer 320: Second anti-reflection layer

[0022] 400: Second electrode layer 500: Protective layer

[0023] 600: Home

[0024] One embodiment of the present invention provides an electrode substrate including a substrate, an engraved groove provided in the substrate, a first anti-reflection layer disposed in the groove, a first electrode layer disposed to cover the first anti-reflection layer and not extending beyond an upper portion of the groove, a second electrode layer having an area overlapping the first electrode layer and disposed on an upper surface of the substrate and a side surface of the groove, and a protective layer disposed to cover at least a portion of the second electrode layer in the groove.

[0025] In one embodiment of the present invention, the engraved groove may include an irregular pattern.

[0026] In one embodiment of the present invention, the pitch of the substrate may be 200 to 1000 μm.

[0027] In one embodiment of the present invention, the first anti-reflection layer may include graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc.

[0028] In one embodiment of the present invention, the first electrode layer may include one or more of copper, nickel, silver, titanium, chromium, molybdenum, gold, and metal alloys thereof.

[0029] In one embodiment of the present invention, the thickness of the second electrode layer may be 50 to 500 nm.

[0030] In one embodiment of the present invention, the protective layer may be disposed on the inside and side of the groove of the second electrode layer.

[0031] In one embodiment of the present invention, the thickness of the protective layer may be less than 1 μm.

[0032] In one embodiment of the present invention, the protective layer may be parallel to the upper surface of the second electrode layer, or the upper surface of the protective layer may have an upward or downward curve.

[0033] One embodiment of the present invention further includes a second anti-reflection layer, and a first metal layer may be disposed between the first anti-reflection layer and the second anti-reflection layer.

[0034] In one embodiment of the present invention, the second anti-reflection layer may include graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc.

[0035] In one embodiment of the present invention, the voltage drop of the electrode substrate may be 3.5 to 10 mV.

[0036] In one embodiment of the present invention, the transmittance of the electrode substrate may be 75% or more.

[0037] Another embodiment of the present invention provides an electrochromic device including the electrode substrate.

[0038] One embodiment of the present invention is illustrated in the accompanying drawings. However, the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. Like reference numerals in the drawings indicate like elements.

[0039] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the invention. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms including "at least one," unless the content clearly dictates otherwise. "At least one" should not be construed as limiting to the singular. As used herein, the term "and / or" includes any and all combinations of one or more of the listed items. The terms "comprises" and / or "comprising" as used in the detailed description specify the presence of stated features, regions, integers, steps, operations, components, and / or ingredients, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, components, ingredients, and / or groups thereof.

[0040] In this specification, reference to "on" or "on" another object includes not only directly on top of the other object, but also cases where an object is interposed between the other object.

[0041] Throughout the specification, when a part is said to be "connected (connected, contacted, coupled)" to another part, this includes not only cases where it is "directly connected" but also cases where it is "indirectly connected" with another part in between.

[0042] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Furthermore, it will be understood that terms defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning within the context of the relevant art and the present disclosure, and not in an idealized or overly formal sense.

[0043] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are not currently anticipated or unforeseen may occur to the applicant or those skilled in the art. Accordingly, the appended claims, as filed and as amended, are intended to encompass all such alternatives, modifications, variations, improvements, and substantial equivalents.

[0044] In the examples below, the terms first, second, etc. are not used in a limiting sense, but are used for the purpose of distinguishing one component from another.

[0045] In the examples below, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0046] For convenience of explanation, the sizes of components in the drawings may be exaggerated or reduced. For example, the sizes and thicknesses of each component shown in the drawings are arbitrarily indicated for convenience of explanation, and thus the present invention is not necessarily limited to what is shown.

[0047] In the following examples, the x-axis, y-axis, and z-axis are not limited to three axes on an orthogonal coordinate system, and can be interpreted in a broad sense that includes them. For example, the x-axis, y-axis, and z-axis may be orthogonal to each other, but may also refer to different directions that are not orthogonal to each other.

[0048] In some embodiments, where implementations are otherwise feasible, specific process sequences may be performed in a different order than described. For example, two processes described in succession may be performed substantially simultaneously, or in a reverse order from the described order.

[0049] An electrode substrate according to one embodiment of the present invention may include a concave groove, a substrate having the groove, a first anti-reflection layer disposed in the groove, a first electrode layer disposed in the groove, a second electrode layer having an area overlapping the first electrode layer, and a protective layer disposed to cover the second electrode layer in the groove.

[0050] FIG. 1 is a cross-sectional view schematically showing an electrode substrate according to one embodiment of the present invention.

[0051] According to FIG. 1, the electrode substrate (10) may include a substrate (100), a first electrode layer (200), a first anti-reflection layer (310), a second electrode layer (400), and a protective layer (500).

[0052] The substrate (100) may have a groove (600), which may be a concave groove. The concave groove may be one or more, and may include an irregular pattern. The substrate may include irregular concave grooves to improve the moiré phenomenon.

[0053] The substrate (100) may be formed of various materials. For example, it may include, but is not limited to, glass, PET (Polyethyleneterephthalate), PU (polyurethane), PC (polycarbonate), PMMA (Acrylic), PVC (PolyVinyl Chloride), PP (PolyPropylene), ABS Resin (Acrylonitrile, Butadiene, Styrene), PA (Polyamide), PE (PolyEthylene), PS (PolyStyrene), PEN (Polyethylene Naphthalate), PES (Polyether Sulfone), COC (Cyclic Olefin Copolymer), TAC (Triacetylcellulose), PVA (Polyvinyl alcohol), PI (Polyimide), POF (Polyolefin), PEEK (Polyetheretherketone), PEI (Polyetherimide), or fluoride resin. According to one embodiment of the present invention, the substrate may be a transparent substrate.

[0054] The pitch of the substrate (100) is 100 to 1000 μm, 100 to 900 μm, 100 to 800 μm, 100 to 700 μm, 100 to 600 μm, 100 to 500 μm, 200 to 1000 μm, 200 to 900 μm, 200 to 800 μm, 200 to 700 μm, 200 to 600 μm, 200 to 500 μm, 400 to 1000 μm, 400 to 900 μm, 400 to 800 μm, 400 to 700 μm, 400 to 600 μm, 400 to 500 μm, 500 to 1000 μm, 500 to 900 μm, 500 to 800 μm, 500 to 700 μm, or 500 to 600 μm, but is not limited thereto.

[0055] The above first anti-reflection layer (310) may be placed in the groove (600) and may be placed in contact with the substrate as shown in FIG. 1, but is not limited thereto.

[0056] The first anti-reflection layer (310) may include, but is not limited to, graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc. According to one embodiment of the present invention, the first anti-reflection layer may be graphite.

[0057] The thickness of the first anti-reflection layer (310) may be, but is not limited to, 2 μm or less, 0.1 to 2 μm, 0.5 to 2 μm, 1 to 2 μm, 1.5 to 2 μm, 0.1 to 1.5 μm, 0.5 to 1.5 μm, 1 to 1.5 μm, 0.1 to 1 μm, 0.5 to 1 μm, 0.1 to 0.6 μm, 0.5 to 0.6 μm, or 0.1 to 0.3 μm.

[0058] As described above, the electrode substrate according to the present invention can reduce light reflection by including a first anti-reflection layer, thereby alleviating the starburst phenomenon.

[0059] The first electrode layer (200) may be arranged to cover the first anti-reflection layer (310) and may not extend beyond the upper portion of the groove (600).

[0060] The first electrode layer (200) may include, but is not limited to, one or more of copper, nickel, silver, titanium, chromium, molybdenum, gold, and metal alloys thereof. According to one embodiment of the present invention, the first electrode layer may include silver.

[0061] The second electrode layer (400) may have an area overlapping with the first electrode layer (200), and may include, as shown in FIG. 1, the upper surface of the substrate (100), the side of the groove (600), and the area overlapping with the first electrode layer (200), but is not limited thereto.

[0062] The second electrode layer (400) is made of ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), FTO (Fluorine Tin Oxide), CuO (tin oxide), Cu2O, ZnO (zinc oxide), TiO2 (titanium oxide), AgO, Ag2O, Ag2O3, Al2O3, WO2, WO3, W2O3, MgO, MoO3, SnO2, In2O3, CrO3, Cr2O3, Sb2O3, Sb2O5, NiO, Cu2O, V2O3, V2O5, CoO, Fe2O3, Fe3O4, Nb2O5, ZAO (Aluminium doped Zinc Oxide), TAO (Aluminum Tin Oxide), ATO (Antimony Tin Oxide), nanowire, photosensitive nanowire film, CNT (Carbon Nano Tube), graphene or their. The second electrode layer may include, but is not limited to, a mixture. According to one embodiment of the present invention, the second electrode layer may be ITO.

[0063] The thickness of the second electrode layer (400) may be, but is not limited to, 50 to 500 nm, 100 to 500 nm, 150 to 500 nm, 50 to 400 nm, 100 to 400 nm, 150 to 400 nm, 50 to 300 nm, 100 to 300 nm, or 150 to 300 nm.

[0064] The above protective layer (500) may be placed inside and on the side of the groove (600) where the second electrode layer (400) is placed, and may be placed on at least a portion of the inside of the groove (600) and the upper surface of the substrate (100) as shown in FIG. 1, but is not limited thereto.

[0065] The above protective layer (500) may include, but is not limited to, carbon nanotubes, PEDOT-PSS, (Poly(3,4-ethylene dioxyhiophene)), polyacetylene, polyaniline, polypyrrole, polypyrrole, polythiophene, polycarbazole derivatives, phenylene vinylene derivatives, acetylene derivatives, phenylenediamine derivatives, phenothiazine derivatives, tetrathiafulvalene derivatives, Poly(fluorine), Polyphenylene, Polypyrene, polyazulene, Polynaphthalene, Poly(pyrrole), Polycabazole, polyindole, polyazepine, Polyaniline, Poly(thiophene), Poly(3,4-ethylenedioxythiophene), Poly(p-phenylene sulfide), Poly(acetylene), or Poly(p-phenylene vinylene). According to one embodiment of the present invention, the protective layer may be carbon nanotubes, PEDOT-PSS, or AgNW.

[0066] The thickness of the protective layer (500) may be less than 1.5 μm, less than 1 μm, 0.2 to 1.5 μm, 0.2 to 1 μm, 0.2 to 0.5 μm, 0.3 to 1.5 μm, 0.3 to 1 μm, or 0.3 to 0.5 μm, but is not limited thereto. According to one embodiment of the present invention, the thickness of the protective layer may be 0.3 to 1 μm.

[0067] The protective layer (500) may be parallel to the upper surface of the second electrode layer (400) as shown in FIG. 1, or the upper surface of the protective layer (500) may have a curved surface upward or downward.

[0068] As described above, the electrode substrate according to the present invention has excellent discoloration and decolorization effects including a protective layer, and when applied to an electrochromic device, reliability can be improved even when repeatedly operated.

[0069] Fig. 2 is a cross-sectional view schematically showing an electrode substrate according to another embodiment of the present invention.

[0070] According to FIG. 2, the electrode substrate (10`) may further include a second anti-reflection layer (320), and a first metal layer (200) may be disposed between the first anti-reflection layer (310) and the second anti-reflection layer (320).

[0071] The second anti-reflection layer (320) may be the same as or different from the first anti-reflection layer (310), and may include graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc. According to one embodiment of the present invention, the second anti-reflection layer may include graphite.

[0072] The thickness of the second anti-reflection layer (320) may be the same as or different from the thickness of the first anti-reflection layer (310). Specifically, the thickness may be 2 μm or less, 0.1 to 2 μm, 0.5 to 2 μm, 1 to 2 μm, 1.5 to 2 μm, 0.1 to 1.5 μm, 0.5 to 1.5 μm, 1 to 1.5 μm, 0.1 to 1 μm, 0.5 to 1 μm, 0.1 to 0.6 μm, 0.5 to 0.6 μm, or 0.1 to 0.3 μm, but is not limited thereto.

[0073] As described above, the electrode substrate according to the present invention can reduce light reflection by including a first anti-reflection layer and a second anti-reflection layer, thereby alleviating the starburst phenomenon. In particular, when a second anti-reflection layer is additionally included as shown in Fig. 2, light reflection can be prevented more effectively.

[0074] In the above drawing 2, the electrode substrate (10`), the first electrode layer (200), the first anti-reflection layer (310), the second electrode layer (400), and the protective layer (500) are the same as those in the above-described embodiment or can be applied with modifications as needed, and a more detailed description is omitted.

[0075]

[0076] Another embodiment of the present invention can provide an electrochromic device including the electrode substrate (10, 10`).

[0077] The above electrochromic element may include a reduction chromic layer and an oxidation chromic layer, and the electrode substrate (10, 10`) may be applied to both the reduction chromic layer and the oxidation chromic layer.

[0078] The voltage drop of the electrode substrate may be, but is not limited to, 3.5 to 10 mV, 4 to 10 mV, 4.5 to 10 mV, 3.5 to 8 mV, 4 to 8 mV, 4.5 to 8 mV, 3.5 to 6 mV, 4 to 6 mV, or 4.5 to 6 mV. According to one embodiment of the present invention, the voltage drop of the electrode substrate may be 3.5 to 5 mV.

[0079] The transmittance of the electrode substrate may be, but is not limited to, 75% or more, 75 to 85%, or 75 to 80%. According to one embodiment of the present invention, the transmittance of the electrode substrate may be 75 to 80%. When the pitch of the substrate in the electrode substrate is 300 μm or less, the transmittance may rapidly decrease.

[0080]

[0081] Hereinafter, the present invention will be described in detail through examples and experimental examples.

[0082] However, the examples and experimental examples described below are only specific examples of one aspect of the present invention, and the present invention is not limited thereto.

[0083]

[0084] <Example 1> Manufacturing of electrode substrate

[0085] To manufacture an electrode substrate according to one embodiment of the present invention, a substrate, a hard mold, and a soft mold were prepared. The substrate was made of PET, the hard mold was made of aluminum, and the soft mold was made of UV resin. The master mold and soft mold included irregular patterns.

[0086] Afterwards, the substrate and mold were laminated and UV irradiated to form irregular engraved grooves. The lamination, cleaning, and sintering processes were then repeated for each of the first antireflection layer, first electrode layer, second electrode layer, and protective layer. The sintering temperature was 100 to 150 degrees Celsius.

[0087] As examples and comparative examples, the products were manufactured with different types and presences of anti-reflection layers, etc.

[0088]

[0089] <Example 2> Manufacturing of an electrochromic device

[0090] After preparing an electrode substrate according to one embodiment of the present invention, the substrate was cleaned with ethanol and acetone. The substrate was then cut and holes were machined. An optically clear adhesive (OCA) film was cut around the outer portion of the discoloration area of ​​the substrate and positioned on each side.

[0091] After the above substrates were bonded in a sandwich configuration, a discoloration solution was injected. The discoloration solution was prepared by mixing an organic reducing discoloration agent (Ethyl viologen dibromide), an oxidizing agent (Dimethylferrocene), a lithium salt, and a solvent. The holes were then sealed to manufacture an electrochromic device.

[0092]

[0093] <Experimental Example 1> Evaluation of Moiré Phenomenon According to Intaglio Pattern

[0094] The moire phenomenon according to the negative pattern of the electrode substrate according to one embodiment of the present invention was evaluated, and the scanning electron microscope (SEM) results are shown in Fig. 3.

[0095] Looking at Figure 3, it can be seen that the moire phenomenon is significantly reduced when the electrode substrate includes grooves of an irregular pattern, as in one embodiment of the present invention, compared to a regular pattern.

[0096]

[0097] <Experimental Example 2> Evaluation of the Starburst Phenomenon According to the Antireflection Layer

[0098] The starburst phenomenon was evaluated according to the presence or absence of an antireflection layer and the number of antireflection layers in an electrode substrate according to one embodiment of the present invention. The results are shown in Fig. 4.

[0099] Referring to Figure 4, it can be seen that the starburst phenomenon is significantly alleviated when an anti-reflection layer is present, particularly when the anti-reflection layer is present only on the lower portion of the first electrode layer or on both sides, as in one embodiment of the present invention. This is confirmed to be due to the blackening process applied to the anti-reflection layer, thereby reducing light reflection.

[0100]

[0101] <Experimental Example 3> Analysis of transmittance and voltage drop

[0102] The transmittance and voltage drop of the electrode substrate according to one embodiment of the present invention were analyzed. The analysis results are shown in Table 1 below.

[0103] Substrate pitch (μm) Line width (μm) Grid voltage drop (mV) TT (%) x (area ratio %) 300 1000 10 2999.16 782 300 900 10 3328.2 377.82.2 300 800 10 3747.3 377.52.5 300 700 10 4286.4 277.22.8 300 600 10 4995.5 76.73.3 3300 500 10 5994.5 8 764 300 400 10 7493.6 6 75.14.9 300 300 10 9992.75 73.46.6 300 200 10 14991.8 370.29.8 300 10 0 10 29990.9 26119

[0104] As shown in Table 1, the transmittance changed depending on the pitch of the substrate, and the transmittance of the electrode substrate according to one embodiment of the present invention was confirmed to be 73 to 80%.

[0105] As shown in Table 1, the voltage drop varied depending on the pitch of the substrate, and in particular, when the pitch was 400 μm and 500 μm, the voltage drop was significantly lower at 3.56 mV and 4.58 mV, respectively.

[0106]

[0107] <Experimental Example 4> Image Analysis According to the Presence or Absence of a Protective Layer

[0108] SEM images of an electrode substrate according to one embodiment of the present invention were analyzed according to the presence or absence of a protective layer. The analysis results are shown in FIGS. 5 to 7.

[0109] Looking at Figures 5a and 5b, it can be confirmed that Ag elution and cracking do not occur when a protective layer is present.

[0110] Looking at Figure 6, it can be seen that when only the second electrode layer exists and no protective layer exists, a crack is formed at the edge, and the crack is created by a scratch.

[0111] Looking at Figure 7, it was confirmed that when only the second electrode layer exists and no protective layer exists, the metal of the first electrode layer is dissolved, causing deterioration.

[0112] Therefore, it can be seen that when a protective layer is additionally included together with the second electrode layer as in one embodiment of the present invention, crack formation and deterioration can be prevented.

[0113] Meanwhile, the discoloration and fading characteristics depending on the presence or absence of a protective layer were confirmed, and the results are shown in Figs. 8 and 9.

[0114] Referring to Figures 8 and 9, it can be seen that the discoloration and bleaching characteristics are reduced when there is no protective layer and when a non-conductive protective layer is present. Therefore, it can be seen that the discoloration and bleaching characteristics are improved when both the second electrode layer and the protective layer are included, as in one embodiment of the present invention, and the protective layer is a conductive protective layer.

[0115]

[0116] <Experimental Example 5> Evaluation of Optimization of Protective Layer Thickness and Content

[0117] The protective layer thickness and protective layer material content were optimized for an electrode substrate according to one embodiment of the present invention, and the results are shown in Fig. 10.

[0118] As shown in Figure 10, as the content of the protective layer material increased, the transmittance decreased, and consequently, the thickness also increased. Considering the transmittance, the optimized thickness of the protective layer was less than 1 μm, and the content of the protective layer material was less than 1%.

[0119]

[0120] <Experimental Example 6> Evaluation of discoloration and fading characteristics according to protective layer type

[0121] Discoloration and decolorization characteristics according to the type of protective layer were evaluated for an electrode substrate according to one embodiment of the present invention, and the results are shown in Table 2 below.

[0122] Type: Discoloration, Discoloration, w / o protective layer 4.548.1PEDOT-PSS 3.645.8CNT 2.742.1AgNW 3.542.5

[0123] In Table 2 above, the discoloration and decolorization effects were evaluated by transmittance (%), and it can be seen that the discoloration and decolorization effects are significantly superior when a protective layer is present compared to when no protective layer is present.

[0124]

[0125] <Experimental Example 7> Reliability Evaluation According to the Presence or Absence of a Protective Layer

[0126] The reliability of an electrochromic device according to one embodiment of the present invention was evaluated according to the presence or absence of a protective layer. The reliability evaluation was conducted by measuring the change in transmittance (ΔT) after repeated operation of the electrochromic device, and the results were normalized and presented in Table 3 and Fig. 11.

[0127] Number of times w / o conductive protective layer w / conductive protective layer 1112001.003841.018964001.00961.042657001.015361.066359000.63341.0663512000.090211.0782

[0128] Looking at Table 3 and FIG. 11 above, it can be confirmed that when an electrochromic device includes a conductive protective layer as in one embodiment of the present invention, ΔT hardly changes even when driving is repeated, so reliability is high.

[0129]

[0130] <Experimental Example 8> Evaluation of the Starburst Phenomenon According to the Type of Antireflection Layer

[0131] The starburst phenomenon was evaluated according to the type of antireflection layer for an electrode substrate according to one embodiment of the present invention. The results are shown in Fig. 12.

[0132] As shown in Figure 12, when the anti-reflection layer is graphite or CuO, the starburst phenomenon is significantly alleviated compared to when it is not present. This is confirmed to be due to the blackening process according to the anti-reflection layer, which reduces light reflection.

[0133]

[0134] <Experimental Example 9> Evaluation of discoloration and decolorization characteristics according to the type of first electrode layer

[0135] The discoloration and decolorization characteristics of the electrode substrate according to one embodiment of the present invention were evaluated according to the type of the first electrode layer, and the results are shown in Table 4 below.

[0136] In case of no discoloration or discoloration of the component, 3977.7Ag4.548.1Cu6.547.5Ni5.849.2CuNi5.049.3

[0137] In Table 4 above, the discoloration and decolorization effects were evaluated by transmittance (%), and it can be seen that the discoloration and decolorization effects are significantly superior when the first electrode layer is present compared to when the first electrode layer is not present.

[0138]

[0139] <Experimental Example 10> Evaluation of discoloration and fading characteristics according to the thickness of the second electrode layer

[0140] The discoloration and decolorization characteristics according to the thickness of the second electrode layer of the electrode substrate according to one embodiment of the present invention were evaluated, and the results are shown in Table 5 below.

[0141] Second electrode layer thickness discoloration and fading If there is no discoloration 2024 (fading is poor) ITO 50 nm 6.6 4 9.1 ITO 200 nm 4.5 4 8.1 ITO 400 nm 4.6 4 6.9 ITO 500 nm 4.7 4.7

[0142] In Table 5 above, the discoloration and decolorization effects were evaluated by transmittance (%), and it can be seen that the discoloration and decolorization effects are significantly superior when the second electrode layer is present when the thickness is 50 to 500 nm compared to when the second electrode layer is not present.

[0143] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0144] The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. Substrate; A concave groove provided within the above substrate; A first anti-reflection layer disposed in the above groove; A first electrode layer arranged to cover the first anti-reflection layer and not extending beyond the upper portion of the groove; A second electrode layer having an area overlapping the first electrode layer and arranged on the upper surface of the substrate and the side surface of the groove; and An electrode substrate comprising a protective layer arranged to cover at least a portion of the second electrode layer in the above groove.

2. In paragraph 1, An electrode substrate, wherein the engraved groove includes an irregular pattern.

3. In paragraph 1, An electrode substrate having a pitch of 200 to 1000 μm.

4. In paragraph 1, An electrode substrate, wherein the first anti-reflection layer comprises graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc.

5. In paragraph 1, An electrode substrate, wherein the first electrode layer comprises at least one of copper, nickel, silver, titanium, chromium, molybdenum, gold, and metal alloys thereof.

6. In paragraph 1, An electrode substrate, wherein the thickness of the second electrode layer is 50 to 500 nm.

7. In paragraph 1, An electrode substrate, wherein the protective layer is disposed on the inside and side of the groove in which the second electrode layer is disposed.

8. In paragraph 1, An electrode substrate, wherein the thickness of the protective layer is less than 1 μm.

9. In paragraph 1, The above protective layer is parallel to the upper surface of the second electrode layer, or An electrode substrate, wherein the upper surface of the protective layer has an upward or downward curve.

10. In paragraph 1, Further comprising a second anti-reflection layer, An electrode substrate, wherein a first metal layer is disposed between the first anti-reflection layer and the second anti-reflection layer.

11. In Article 10, An electrode substrate, wherein the second anti-reflection layer comprises graphite, copper oxide (CuO), magnetite (Fe3O4), copper selenide (Cu2Se), or black oxide of zinc.

12. In paragraph 1, An electrode substrate having a voltage drop of 3.5 to 10 mV.

13. In paragraph 1, An electrode substrate having a transmittance of 75% or more.

14. An electrochromic device comprising an electrode substrate according to any one of claims 1 to 13.

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