KR20170112384A - An Electrochromic Device - Google Patents
An Electrochromic Device Download PDFInfo
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- KR20170112384A KR20170112384A KR1020160039383A KR20160039383A KR20170112384A KR 20170112384 A KR20170112384 A KR 20170112384A KR 1020160039383 A KR1020160039383 A KR 1020160039383A KR 20160039383 A KR20160039383 A KR 20160039383A KR 20170112384 A KR20170112384 A KR 20170112384A
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- layer
- electrochromic device
- electrolyte
- electrochromic
- oxide
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- 238000003860 storage Methods 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims description 47
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- 238000000034 method Methods 0.000 claims description 28
- -1 copper nitride Chemical class 0.000 claims description 27
- 238000004040 coloring Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- 238000002834 transmittance Methods 0.000 claims description 22
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- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
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- 229910012424 LiSO 3 Inorganic materials 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 4
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- 238000000151 deposition Methods 0.000 claims description 3
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- 239000011244 liquid electrolyte Substances 0.000 claims description 3
- 229910010238 LiAlCl 4 Inorganic materials 0.000 claims description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
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- 239000002200 LIPON - lithium phosphorus oxynitride Substances 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
본 출원은 전기변색소자 및 그 제조방법에 관한 것이다. 신규한 이온저장층 물질을 사용하는 본 출원은 내구성 및 박막 생산성이 우수하고, 종래 기술 대비 변색속도가 개선된 전기변색소자를 제공한다.The present application relates to an electrochromic device and a manufacturing method thereof. The present application using a novel ion storage layer material provides an electrochromic device having excellent durability and thin film productivity and improved color change rate compared to the prior art.
Description
본 출원은 전기변색소자에 관한 것이다. 구체적으로, 본 출원은 변색 효율 및 스위칭 타임이 개선된 전기변색소자에 관한 것이다.The present application relates to an electrochromic device. Specifically, the present application relates to an electrochromic device having improved color fading efficiency and switching time.
전기변색(Electrochromism)은, 전기화학적 산화 및 환원 반응에 따라 전기변색 활성물질의 색이나 광 투과도와 같은 광학적 성질이 변하는 현상을 말한다. 이러한 현상을 이용한 전기 변색 소자는 적은 비용으로도 넓은 면적의 소자로 제조될 수 있고, 낮은 소비전력을 갖기 때문에, 스마트 윈도우, 스마트 거울, 전자종이 등과 같은 다양한 분야에서 주목 받고 있다.Electrochromism is a phenomenon in which optical properties such as color and light transmittance of an electrochromic active material are changed by electrochemical oxidation and reduction reactions. Electrochromic devices using such a phenomenon are attracting attention in various fields such as smart windows, smart mirrors, and electronic paper because they can be manufactured with a small area and have low power consumption.
도 1은 일반적인 전기변색소자의 단면도이다. 도면에서와 같이, 전기변색소자(100)는 제1 전극층(110), 상기 제1 전극층(110) 상에 마련된 전기변색층(120), 상기 전기변색층 상에 마련된 전해질층(130), 상기 전해질층 상에 마련된 이온저장층(140), 및 상기 이온저장층 상에 마련된 제2 전극층(150)을 포함할 수 있다. 도시하지 않았으나, 각 전극(110, 150)의 외측면에는, 투명한 유리 또는 고분자 수지로부터 형성된 기판이 추가로 포함될 수 있다. 1 is a cross-sectional view of a general electrochromic device. As shown in the figure, the
일반적으로 전기변색층 및/또는 이온저장층은 산화텅스텐이나 리튬니켈산화물과 같은 무기물질을 전기변색물질로서 포함할 수 있다. 구체적으로, 특정 전위가 전극에 인가될 경우, H+, 또는 Li+, Na+와 같은 전해질 이온이 전해질층을 거쳐 전기변색층과 이온저장층 사이를 이동하고, 동시에 외부 회로를 통해 전자가 전기변색층에 주입되거나 전기변색층으로부터 이탈하게 되면서, 전기변색물질의 산화/환원 반응이 교대되고, 전기변색층이나 이온저장층의 착색(coloring) 또는 탈색(bleaching)이 이루어 진다. 이렇듯, 전기변색소자의 광학 특성 변화에는 이온 물질의 이동이 전제되기 때문에, 변색 에는 소정의 시간, 즉 스위칭 타임(switching time)이 소요되고, 그에 따라 변색시간을 줄일 수 있는 기술이 요구된다.In general, the electrochromic layer and / or the ion storage layer may contain an inorganic substance such as tungsten oxide or lithium nickel oxide as an electrochromic material. Specifically, when a specific potential is applied to the electrode, electrolyte ions such as H + or Li + and Na + move between the electrochromic layer and the ion storage layer through the electrolyte layer, and at the same time, The oxidation / reduction reaction of the electrochromic material alternates and the coloring or bleaching of the electrochromic layer or the ion storage layer is performed as the electrochromic material is injected or separated from the electrochromic layer. As described above, since the movement of the ionic material is presupposed in the change of the optical characteristic of the electrochromic device, there is a need for a technique which can take a predetermined time, that is, a switching time, and thereby reduce the discoloration time.
본 출원의 일 목적은 변색효율이 우수하고, 변색속도가 개선된 전기변색소자를 제공하는 것이다.An object of the present invention is to provide an electrochromic device excellent in discoloration efficiency and improved in discoloration rate.
본 출원의 다른 목적은 박막으로도 충분한 변색 효과를 갖는 전기변색소자를 제공하는 것이다.Another object of the present invention is to provide an electrochromic device having a sufficient discoloring effect even in a thin film.
본 출원의 상기 목적 및 그 외 기타 목적은 하기 상세히 설명되는 본 출원에 의해 모두 해결될 수 있다.These and other objects of the present application can be resolved by the present application, which is described in detail below.
본 출원은 전기변색소자에 관한 것이다. 상기 전기변색소자는 대향하는 2개의 전극, 전기변색층, 전해질층 및 이온저장층을 포함할 수 있다.The present application relates to an electrochromic device. The electrochromic device may include two opposing electrodes, an electrochromic layer, an electrolyte layer, and an ion storage layer.
전극은 전기변색층에 전하를 공급할 수 있는 구성을 의미할 수 있다, 하나의 예시에서, 상기 전극은 투명 전도성 산화물(Transparent Conductive Oxide, TCO), 전도성 고분자, 은나노 와이어(Ag Nanowire), 또는 메탈메쉬(Metal mesh) 중 어느 하나 이상을 포함하여 형성될 수 있다. 보다 구체적으로, ITO(Indium Tin Oxide), FTO(Fluor doped Tin Oxide), AZO(Aluminium doped Zinc Oxide), GZO(Galium doped Zinc Oxide), ATO(Antimony doped Tin Oxide), IZO(Indium doped Zinc Oxide), NTO(Niobium doped Titanium Oxide), ZnO, OMO(Oxide/Metal/Oxide) 또는 CTO 등이 전극물질로서 사용될 수 있으나, 이에 제한되는 것은 아니다. 또 다른 예시에서, 상기 전극층은 2 이상의 전극 물질이 복수 개의 층으로 적층된 구조를 가질 수 있다.In one example, the electrode may be a transparent conductive oxide (TCO), a conductive polymer, a silver nanowire, or a metal mesh And a metal mesh. More specifically, it is possible to use a metal oxide such as ITO (indium tin oxide), FTO (fluoro-doped tin oxide), AZO (aluminum doped zinc oxide), GZO (gallium doped zinc oxide), ATO (antimony doped tin oxide), IZO , Niobium doped titanium oxide (NTO), ZnO, oxide / metal / oxide (OMO), or CTO may be used as the electrode material. In another example, the electrode layer may have a structure in which two or more electrode materials are stacked in a plurality of layers.
상기 전극층을 형성하는 방법은 특별히 제한되지 않으며, 공지된 방법이 제한 없이 사용될 수 있다. 예를 들어, 스퍼터링 공정을 통해, 투명 전도성 산화물 입자를 포함하는 전극 재료를, 투명한 유리 기판상에 박막형태로 형성함으로써, 전극층이 마련될 수 있다. 상기 전극층은 1 nm 내지 1 ㎛ 범위 내에서, 150 nm 이상, 200 nm 이상, 또는 300 nm 이상의 두께를 가질 수 있다. 전극층 두께의 상한은 특별히 제한되지 않으나, 저 저항 구현을 위해 상기 전극층은 800 nm 이하, 700 nm 이하, 또는 500 nm 이하의 두께를 가질 수 있다.The method for forming the electrode layer is not particularly limited, and known methods can be used without any limitation. For example, an electrode layer can be provided by forming an electrode material containing transparent conductive oxide particles in a thin film form on a transparent glass substrate through a sputtering process. The electrode layer may have a thickness of 150 nm or more, 200 nm or more, or 300 nm or more in the range of 1 nm to 1 占 퐉. The upper limit of the thickness of the electrode layer is not particularly limited, but the electrode layer may have a thickness of 800 nm or less, 700 nm or less, or 500 nm or less for low resistance implementation.
하나의 예시에서, 상기 전극층은 가시광선에 대하여 70 % 내지 95% 범위의 광 투과율을 가질 수 있다. 본 출원에서 가시광선이란 약 350 nm 내지 750 nm 범위의 파장을 갖는 광을 의미할 수 있으며, 보다 구체적으로는 550 nm 파장의 광을 의미할 수 있다.In one example, the electrode layer may have a light transmittance in the range of 70% to 95% with respect to visible light. The visible light in the present application may mean light having a wavelength in the range of about 350 nm to 750 nm, and more specifically, light having a wavelength of 550 nm.
전기변색층은 전기신호에 따라 색이 변하는 전기변색물질을 포함할 수 있다. 사용 가능한 전기변색물질로는 전도성 고분자, 유기변색 물질 및/또는 무기변색 물질을 예로 들 수 있다. 상기 전도성 고분자로는 폴리피롤, 폴리아닐린, 폴리피리딘, 폴리인돌, 폴리카바졸 등이 사용될 수 있고, 유기변색 물질로는 비올로겐, 안트라퀴논, 페노사이아진과 같은 물질이 사용될 수 있으나 이에 제한되는 것은 아니다.The electrochromic layer may include an electrochromic material whose color changes depending on an electrical signal. Examples of usable electrochromic materials include conductive polymers, organic coloring materials and / or inorganic coloring materials. As the conductive polymer, polypyrrole, polyaniline, polypyridine, polyindole, polycarbazole, or the like can be used. As the organic coloring material, materials such as viologen, anthraquinone, phenothiazine and the like can be used. no.
하나의 예시에서, 상기 전기변색층은 Ti, Nb, Mo, Ta, W, V, Cr, Mn, Fe, Co, Ni, Rh, 및 Ir 의 산화물 중 하나 이상의 산화물을 무기변색 물질로 포함할 수 있다. 보다 구체적으로, TiO2 , Nb2O5, MoO3, Ta2O5, WOx, V2O5 , CrO3 , LixCoO2 , NiO, LiNiOx, Rh2O3, 또는 IrO2 등이 사용 가능한 무기변색 물질일 수 있으나, 이에 제한되는 것은 아니다.In one example, the electrochromic layer may include an oxide of at least one of Ti, Nb, Mo, Ta, W, V, Cr, Mn, Fe, Co, Ni, Rh, have. More specifically, TiO 2, Nb 2 O 5 , MoO 3, Ta 2 O 5, WO x, V 2 O 5, CrO 3, Li x CoO 2, NiO, LiNiO x, Rh 2 O 3, or IrO 2, etc. May be, but are not limited to, the usable inorganic discoloration material.
보다 구체적으로, 본 출원의 전기변색층은 텅스텐산화물(WOx)을 전기변색물질로 포함할 수 있다. 상기 텅스텐산화물(WOx)은 하기와 같은 반응을 통해 착색 또는 탈색될 수 있다. 하기 반응식에서, M은 H+, Li+, 또는 Na+와 같은 전해질 이온일 수 있다.More specifically, the electrochromic layer of the present application may contain tungsten oxide (WO x ) as an electrochromic material. The tungsten oxide (WO x ) may be colored or discolored through the following reaction. In the following scheme, M may be an electrolyte ion such as H + , Li + , or Na + .
[반응식][Reaction Scheme]
WO3 (탈색: 투명) + xe- + xM+ ⇔ MxWO3 (착색: 파란색)WO 3 (discoloration: transparent) + xe - + xM + ⇔ M x WO 3 (coloring: blue)
상기 반응에서, 전기변색층이 탈색된 경우 전기변색소자는 입사광을 투과시키게 되고, 착색된 경우에는 입사광의 투과량이 줄어들게 되면서 전기변색소자의 광학특성이 변화될 수 있다. 상기 착색과 탈색 반응은 인가되는 전압의 극성(또는 전류의 흐름 방향)에 따라 교대로 일어날 수 있다.In the above reaction, when the electrochromic layer is discolored, the electrochromic device transmits incident light. When the electrochromic device is colored, the amount of incident light is reduced, so that the optical characteristics of the electrochromic device can be changed. The coloring and decoloring reactions may occur alternately according to the polarity of the applied voltage (or the flow direction of the current).
하나의 예시에서, 전기변색층은 착색시 가시광선에 대한 투과율이 10 % 내지 50 %이고, 탈색시 가시광선에 대한 투과율이 45 % 내지 85 % 범위일 수 있다.In one example, the electrochromic layer may have a transmittance of 10% to 50% with respect to visible light upon coloring and a transmittance of 45% to 85% with respect to visible light upon decolorization.
하나의 예시에서, 전기변색층은 그 두께가 50 nm 내지 400 nm일 수 있다. 상기 두께가 50nm 미만일 경우 변색을 위한 반응이 충분히 일어나기 어렵고, 400 nm를 초과할 경우에는 박막의 전기변색소자를 제공할 수 없다. In one example, the electrochromic layer may have a thickness of 50 nm to 400 nm. When the thickness is less than 50 nm, the reaction for discoloration is difficult to occur sufficiently, and when the thickness is more than 400 nm, a thin film electrochromic device can not be provided.
이온저장층은, 전기변색층의 산화환원반응에 필요한 전하 입자가 삽입 또는 탈리될 수 있어, 변색 반응에 관여할 수 있는 층을 의미할 수 있다. 종래기술에서는, 상기 이온저장층의 역할을 고려하여, 상보적인 전기변색물질을 전기변색층과 이온저장층 각각에 사용하였다. 예를 들어, 전기변색층에 산화텅스텐(WOx)과 같은 환원성 변색 물질이 포함된 경우, 이온저장층에는 리튬니켈산화물(LiNiOx)과 같은 산화성 변색 물질이 포함되었다. 그러나, 상기와 같은 구성을 갖는 전기변색소자는 변색효율이 좋지 못하고, 스위칭 타임(switching time)이 느린 단점이 있다.The ion storage layer may mean a layer that can be inserted or removed from the charge particles necessary for the oxidation-reduction reaction of the electrochromic layer, and can participate in the discoloration reaction. In the prior art, a complementary electrochromic material was used for each of the electrochromic layer and the ion storage layer in consideration of the role of the ion storage layer. For example, when the electrochromic layer contains a reducing discoloration substance such as tungsten oxide (WO x ), the ion storage layer contains an oxidative discoloring substance such as lithium nickel oxide (LiNiO x ). However, the electrochromic device having the above-described structure has a disadvantage that the coloring efficiency is poor and the switching time is slow.
본 출원은, 변색효율 및 스위칭 타임을 개선하고자, 질화구리(CuNx)를 이온저장층에 포함할 수 있다. 질화구리(CuNx)는 박막 증착성이 우수할 뿐 아니라, 100 nm 이하의 두께에서도 전하를 충분히 수용하고 저장할 수 있기 때문에, 소자의 변색 및 탈색 사이에 소요되는 스위칭 타임을 줄일 수 있다.The present application may include copper nitride (CuN x ) in the ion storage layer to improve the discoloration efficiency and the switching time. Copper nitride (CuN x ) not only has excellent thin film deposition properties but also can sufficiently store and store charges even at a thickness of 100 nm or less, so that the switching time required for discoloration and discoloration of the device can be reduced.
하나의 예시에서, 상기 질화구리(CuNx)로는 구리와 질소의 질량비가 0.01 ≤ N/Cu ≤ 0.3 범위인 질화구리가 사용될 수 있다. 보다 구체적으로, 0.05 ≤ N/Cu ≤ 0.20 범위인 질화구리가 사용될 수 있다. 상기 N/Cu 의 질량비가 0.2를 초과할 경우 질화구리(CuNx) 박막이 열역학적으로 불안정하기 때문에 이온저장층을 제조하기 어려울 수 있고, 질량비가 0.05 미만일 경우에는 금속 특성이 우세하여 투명 박막을 구현하기가 어려울 수 있다.In one example, as the copper nitride (CuN x ), copper nitride having a mass ratio of copper to nitrogen in the range of 0.01? N / Cu? 0.3 may be used. More specifically, copper nitrides having a range of 0.05? N / Cu? 0.20 may be used. If the mass ratio of N / Cu exceeds 0.2, the CuN x thin film may be thermodynamically unstable. Therefore, it may be difficult to produce an ion storage layer. When the mass ratio is less than 0.05, the metal characteristic is dominant, It can be difficult to do.
하나의 예시에서, 상기 이온저장층은 1,000 ohm/sq 이하의 저항을 가질 수 있다. 저항값이 상기 범위인 경우, 이온저장층의 전기적 특성을 개선하여 응답속도를 높이고 스위칭 타임을 낮추는데 기여할 수 있다.In one example, the ion storage layer may have a resistance of less than or equal to 1,000 ohm / sq. When the resistance value is within the above range, it is possible to improve the electrical characteristics of the ion storage layer, thereby increasing the response speed and reducing the switching time.
상기 질화구리(CuNx)를 포함하는 이온저장층에 대하여, 광 투과 특성, 즉 투명한 성질을 부여하기 위해서, 이온저장층의 두께를 150 nm 이하로 형성할 수 있다. 예를 들어, 120 nm 이하, 100 nm 이하, 80 nm 이하, 또는 50 nm 이하로 이온저장층을 형성할 수 있다. 상기 두께의 하한은 특별히 한정되지 않으나, 10 nm 이상의 범위로 형성될 수 있다. 본 출원의 이온저장층은, 상기 두께 범위에서도, 전기변색물질의 산화 및 환원 반응에 요구되는 충분한 이온 저장능을 가질 수 있을 뿐 아니라, 변색 또는 탈색되지 않고 일정한 광 투과성을 갖기 때문에, 전기변색층의 착색 또는 탈색이 이온저장층에 의해 왜곡되지 않고 소자에 충분히 반영할 수 있다.The thickness of the ion storage layer may be 150 nm or less in order to impart the light transmitting property, that is, the transparent property, to the ion storage layer containing copper nitride (CuN x ). For example, the ion storage layer can be formed to 120 nm or less, 100 nm or less, 80 nm or less, or 50 nm or less. The lower limit of the thickness is not particularly limited, but may be in the range of 10 nm or more. The ion storage layer of the present application can not only have sufficient ion storage capacity required for the oxidation and reduction reaction of the electrochromic material, but also has a constant light transmittance without discoloration or discoloration, Can be sufficiently reflected on the device without being distorted by the ion storage layer.
하나의 예시에서, 상기 이온저장층의 가시광선에 대한 투과율은 그 상한이, 95% 이하, 90% 이하, 또는 80% 이하일 수 있으며, 그 하한은 60% 이상, 또는 70% 이상일 수 있다. 또한, 상기 이온저장층의 가시광선에 대한 굴절률은 2.0 내지 3.5일 수 있다.In one example, the transmittance of the ion storage layer to visible light may be up to 95%, 90%, or 80%, and the lower limit may be 60% or more, or 70% or more. The refractive index of the ion storage layer with respect to visible light may be 2.0 to 3.5.
전해질층은 리튬이온(Li+)과 같이 전기변색 반응에 관여하는 이온을 포함할 수 있다. 전해질층에 포함되는 전해질의 종류는 특별히 제한되지 않으며, 액체 전해질, 겔-고분자 전해질 또는 무기 고체 전해질일 수 있다.The electrolyte layer may include ions involved in the electrochromic reaction such as lithium ion (Li < + & gt ; ). The type of the electrolyte contained in the electrolyte layer is not particularly limited and may be a liquid electrolyte, a gel-polymer electrolyte, or an inorganic solid electrolyte.
하나의 예시에서, 상기 전해질이 겔-고분자 전해질인 경우, 상기 전해질층은 카보네이트 화합물과 리튬화합물을 포함하는 조성물의 경화물을 포함할 수 있다. 카보네이트계 화합물은 유전율이 높기 때문에, 리튬염이 제공하는 이온의 전도도를 높일 수 있다. 예를 들어, PC(propylene carbonate), EC(ethylene carbonate), DMC(dimethyl carbonate), DEC(diethyl carbonate) 및 EMC(ethylmethyl carbonate)와 같은 카보네이트계 화합물이 사용될 수 있으나 이에 제한되는 것은 아니다. 리튬화합물로는 LiF, LiCl, LiBr, LiI, LiClO4, LiBF4, LiClO3, LiAsF6, LiSbF6, LiAl04, LiAlCl4, LiNO3, LiN(CN)2, LiPF6, Li(CF3)2PF4, Li(CF3)3PF3, Li(CF3)4PF2, Li(CF3)5PF, Li(CF3)6P, LiSO3CF3, LiSO3C4F9, LiSO3(CF2)7CF3, 또는 LiN(SO2CF3)2, 등을 예로 들 수 있으나, 이에 제한되지 않는다. In one example, when the electrolyte is a gel-polymer electrolyte, the electrolyte layer may comprise a cured product of a composition comprising a carbonate compound and a lithium compound. Since the carbonate compound has a high dielectric constant, the conductivity of the ions provided by the lithium salt can be increased. For example, carbonate compounds such as PC (propylene carbonate), EC (ethylene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate) and EMC (ethylmethyl carbonate) may be used. Lithium compounds are LiF, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiClO 3, LiAsF 6, LiSbF 6, LiAl0 4, LiAlCl 4, LiNO 3, LiN (CN) 2, LiPF 6, Li (CF 3) 2 PF 4, Li (CF 3 ) 3 PF 3, Li (CF 3) 4 PF 2, Li (CF 3) 5 PF, Li (CF 3) 6 P, LiSO 3 CF 3, LiSO 3 C 4 F 9, LiSO 3 (CF 2 ) 7 CF 3 , or LiN (SO 2 CF 3 ) 2 , and the like.
또 하나의 예시에서, 상기 전해질이 무기 고체전해질일 경우, 상기 전해질층은 소위 LIPON(Lithium Phosphorous Oxynitride)으로 불리는 리튬 포스포러스 옥시나이트라이드 또는 리튬이온이 도핑된 전이금속 산화물, 또는 Ta2O5을 포함할 수 있다. 구체적으로, 상기 전해질층은 몰리브덴(Mo), 탄탈(Ta), 지르코늄(Zr), 하프늄(Hf) 및 텅스텐(W)과 같은 전이금속 산화물에 리튬 금속이 도핑된 고체전해질 일 수 있다. 겔 폴리머의 경우 충방전 사이클이 증가함에 따라 버블이 발생하고 그 내구성이 저하되는 반면, 무기 고체전해질을 사용할 경우에는 버블 발생이 없기 때문에 소자의 내구성과 수명을 증가시킬 수 있다.In another example, when the electrolyte is an inorganic solid electrolyte, the electrolyte layer may be made of a lithium phosphorus oxynitride or lithium ion-doped transition metal oxide called LIPON (Lithium Phosphorous Oxynitride), or Ta 2 O 5 . Specifically, the electrolyte layer may be a solid electrolyte in which lithium metal is doped in a transition metal oxide such as molybdenum (Mo), tantalum (Ta), zirconium (Zr), hafnium (Hf), and tungsten (W). In the case of the gel polymer, bubbles are generated and durability is lowered as the charge / discharge cycle is increased. On the other hand, when the inorganic solid electrolyte is used, the durability and lifetime of the device can be increased because no bubbles are generated.
상기 전해질층은 30 ㎛ 내지 200 ㎛ 범위의 두께를 가질 수 있고, 가시광선에 대한 투과율이 70 % 내지 95 % 범위일 수 있다.The electrolyte layer may have a thickness in the range of 30 [mu] m to 200 [mu] m, and the transmittance to visible light may range from 70% to 95%.
본 출원의 전기변색소자는 전원을 추가로 포함할 수 있다. 예를 들어, 상기 전원은, 외부회로를 통해 전극층에 전기적으로 연결될 수 있다. 전압을 인가하기 위한 장치나 방식은 당업자에 의해 적절히 선택될 수 있으며, 특별히 제한되지 않는다.The electrochromic device of the present application may further include a power source. For example, the power source may be electrically connected to an electrode layer through an external circuit. Apparatuses and methods for applying a voltage can be appropriately selected by a person skilled in the art and are not particularly limited.
하나의 예시에서, 상기 전원은, 전기변색소자에 대하여 2V 이하 크기의 착색 전위를 인가할 수 있고, 마찬가지로 2V이하 크기의 탈색 전위를 인가할 수 있다. 본 출원의 경우, 전기변색층만이 인가되는 전압에 따라 착색 또는 탈색되고, 이온저장층은 착색 또는 탈색 없이 일정 범위의 광 투과율을 가질 수 있다. 보다 구체적으로, WOx를 포함하는 층, 즉 전기변색층이 직접 적층된 전극층에 음(-)의 부호를 갖는 착색 전위가 2V 이하 크기로 인가될 경우, 리튬이온이 삽입되면서 전기변색층이 착색되고, 상기 전기변색층이 착색되는 시간(duration time) 동안, 이온저장층에 포함된 질화구리(CuNx)는 변색 없이 투명성을 유지하면서 이온저장층으로서의 역할을 수행할 수 있다. 반대로, 전기변색 소자가 탈색되기 위해서는, WOx를 포함하는 전기변색층이 적집 적층된 전극층에 양(+)의 부호를 갖는 탈색 전위를 2V 이하의 크기로 인가시켜야 한다. 착색 및 탈색 전압의 크기가 2V를 초과할 경우 질화구리(CuNx)의 변색이 유발되면서 이온저장층으로의 역할을 충분히 수행하기 어렵다. 상기 범위의 전압이 인가되는 경우, 전기변색층의 착탈색 반응과 무관하게, 이온저장층은 광학 특성의 큰 변화 없이 가시광선에 대하여 60 % 내지 80% 범위의 투과율을 유지할 수 있다.In one example, the power source can apply a coloring potential of 2 V or less to the electrochromic device, and similarly, a decoloring potential of 2 V or less can be applied. In the case of this application, only the electrochromic layer is colored or discolored depending on the applied voltage, and the ion storage layer can have a certain range of light transmittance without coloring or discoloring. More specifically, when a coloring potential having negative (-) sign is applied to a layer containing WO x , that is, an electrode layer directly stacked with an electrochromic layer, with a size of 2 V or less, lithium ions are inserted, (CuN x ) contained in the ion storage layer can function as an ion storage layer while maintaining transparency without discoloration during the duration time of coloring the electrochromic layer. On the other hand, in order for the electrochromic device to decolorize, the decoloring potential having positive (+) sign should be applied to the electrode layer in which the electrochromic layer containing WO x is laminated in a size of 2 V or less. When the coloring and decoloring voltage exceeds 2V, it causes discoloration of copper nitride (CuN x ), and thus it is difficult to sufficiently function as an ion storage layer. When the voltage in the above range is applied, irrespective of the color reaction of the electrochromic layer, the ion storage layer can maintain a transmittance in the range of 60% to 80% with respect to visible light without a large change in optical characteristics.
본 출원의 다른 일례에서, 본 출원은 전기변색소자의 제조방법에 관한 것이다. 보다 구체적으로, 상기 제조방법은, 하나의 전극층 상에 구리와 질소의 질량비가 0.05 ≤ N/Cu ≤ 0.20 범위를 갖는 질화구리(CuNx)층을 마련하는 단계, 및 다른 하나의 전극층 상에 텅스텐산화물(WOx)층을 마련하는 단계를 포함할 수 있다. 상기 설명된 바와 같이, 질화구리(CuNx)층은 본 출원 전기변색소자에서 이온저장층으로서 사용될 수 있고, 상기 텅스텐산화물(WOx)층은 전기변색층으로 사용될 수 있다. 전극층, 이온저장층 및 전기변색층의 구성이나 그 밖의 특성은 상기 언급된 바와 동일하다.In another example of this application, the present application relates to a method of manufacturing an electrochromic device. More specifically, the manufacturing method comprises the steps of: providing a copper nitride (CuN x ) layer having a copper / nitrogen mass ratio in the range of 0.05? N / Cu? 0.20 on one electrode layer; and a tungsten Oxide (WO x ) layer. As described above, a copper nitride (CuN x ) layer can be used as an ion storage layer in the present electrochromic device, and the tungsten oxide (WO x ) layer can be used as an electrochromic layer. The structure and other properties of the electrode layer, ion storage layer and electrochromic layer are the same as those mentioned above.
상기 각 층을 마련하는 방법은 특별히 제한되지 않으며, 공지된 방법을 사용할 수 있다. 예를 들어, 증착(deposition), 스핀코팅(spin coating), 딥코팅(dip coating), 스크린 인쇄, 그라비아 코팅, 졸겔(sol-Gel)법, 또는 슬롯 다이 코팅(slot die) 중 어느 하나의 방법에 의해 각 층이 마련될 수 있다. 증착의 경우, 물리 기상 증착법(Physical Vapor Deposition, PVD)이나 화학 기상 증착법(Chemical Vapor Deposition, CVD)에 의해 이루어질 수 있다. 사용가능한 물리기상 증착법으로는 스퍼터링(Sputtering)법, 전자-빔 증착법(E-beam evaporation), 열 증착법(Thermal evaporation), 레이저 분자 빔 증착법(Laser Molecular Beam Epitaxy, L-MBE) 또는 펄스 레이저 증착법(Pulsed Laser Deposition, PLD) 등을 예로 들 수 있고, 화학 기상 증착법으로는 열 화학 기상 증착법(Thermal Chemical Vapor Deposition), 플라즈마 화학 기상 증착법(Plasma-Enhanced Chemical Vapor Deposition, PECVD), 광 화학 기상 증착법(Light Chemical Vapor Deposition), 레이저 화학 기상 증착법(Laser Chemical Vapor Deposition), 금속-유기 화학 기상 증착법(Metal-Organic Chemical Vapor Deposition, MOCVD), 또는 수소화물 기상 증착법(Hydride Vapor Phase Epitaxy, HVPE) 등을 예로 들 수 있으나 이에 제한되는 것은 아니다.The method of forming each layer is not particularly limited, and a known method can be used. For example, any one of a deposition method, a spin coating method, a dip coating method, a screen printing method, a gravure coating method, a sol-Gel method, or a slot die coating method Each layer may be provided. The deposition can be performed by physical vapor deposition (PVD) or chemical vapor deposition (CVD). Examples of the physical vapor deposition method that can be used include a sputtering method, an E-beam evaporation method, a thermal evaporation method, a laser molecular beam epitaxy (L-MBE) method, or a pulsed laser deposition method Pulsed Laser Deposition (PLD)). Examples of the chemical vapor deposition method include a thermal chemical vapor deposition method, a plasma enhanced chemical vapor deposition (PECVD) method, a light chemical vapor deposition method (Light Chemical Vapor Deposition) Chemical vapor deposition (CVD), Laser Chemical Vapor Deposition, Metal-Organic Chemical Vapor Deposition (MOCVD), or Hydride Vapor Phase Epitaxy (HVPE) But is not limited thereto.
하나의 예시에서, 질화구리(CuNx)층은 스퍼터링 방식에 의해 전극층의 일면에 증착될 수 있다. 보다 구체적으로, 대략 30 내지 60 nm 두께의 Cu 타겟(target)이 형성되고, 5 mTorr 내지 60 mTorr 공정압을 갖는 챔버에서, 100 W 내지 300 W의 파워를 가하고, 질소(N2)가스 및 아르곤(Ar) 가스를 각각 5 sccm 내지 25 sccm 및 15 sccm 내지 45 sccm 유량으로 공급하는 공정을 통해, 질화구리(CuNx)층을 전극층 상에 마련할 수 있다. 이때, 챔버 내에 공급되는 기체 중 질소의 분압은 40% 이상일 수 있으나, 특별히 제한되는 것은 아니다.In one example, a copper nitride (CuN x ) layer can be deposited on one side of the electrode layer by a sputtering process. More specifically, a power of 100 W to 300 W is applied in a chamber in which a Cu target of approximately 30 to 60 nm thickness is formed and a process pressure of 5 mTorr to 60 mTorr is applied and a nitrogen (N 2 ) gas and argon (CuN x ) layer can be provided on the electrode layer through a process of supplying Ar gas at a flow rate of 5 sccm to 25 sccm and a flow rate of 15 sccm to 45 sccm, respectively. At this time, the partial pressure of nitrogen in the gas supplied into the chamber may be 40% or more, but is not particularly limited.
본 출원의 제조방법은, 질화구리(CuNx)층 또는 산화텅스텐층의 일면에 전해질층을 마련하는 단계를 추가로 포함할 수 있다. 전해질층에 사용될 수 있는 전해질의 종류는 상기 언급된 바와 같다.The manufacturing method of the present application may further include the step of providing an electrolyte layer on one side of a copper nitride (CuN x ) layer or a tungsten oxide layer. The kind of the electrolyte that can be used for the electrolyte layer is as mentioned above.
신규한 이온저장층 물질을 포함하는 본 출원은, 박막 생산성이 우수할 뿐 아니라, 변색효율이 개선되어 변색속도가 단축된 전기변색소자를 제공할 수 있다.The present application including a novel ion storage layer material can provide an electrochromic device having not only excellent thin film productivity but also improved color fading efficiency and shortened color fading rate.
도 1은 일반적인 전기변색소자의 단면도를 개략적으로 도시한다.Fig. 1 schematically shows a cross-sectional view of a general electrochromic device.
이하, 실시예를 통해 본 출원을 상세히 설명한다. 그러나, 본 출원의 보호범위가 하기 설명되는 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present application will be described in detail by way of examples. However, the scope of protection of the present application is not limited by the embodiments described below.
실험례Experimental Example 1: 하프-셀(Half-Cell)의 광학 특성 및 구동 특성 측정 1: Measurement of optical characteristics and driving characteristics of half-cell
하기와 같이 제조된 하프-셀에 대하여, potentiostat 장비(Princeton Applied Research, PMC-1000) 및 UV-vis spectrometer 장비(Solidspec 3700)를 이용하여 각 셀의 구동특성 및 광학특성을 25℃ 온도에서 측정하였다. 착색 및 탈색 전위로 각각 2V 전압을 인가하였다. 이때, 사용된 각 시편의 크기는 2.0 cm X 10 cm = 20 cm2로 일치시켰다. 그 결과는 하기 표 1과 같다.The driving characteristics and the optical characteristics of each cell were measured at a temperature of 25 ° C using a potentiostat apparatus (Princeton Applied Research, PMC-1000) and a UV-vis spectrometer apparatus (Solidspec 3700) . And a voltage of 2 V was applied to each of the coloring and decoloring potentials. At this time, the size of each specimen used was matched to 2.0 cm × 10 cm = 20 cm 2 . The results are shown in Table 1 below.
실시예Example
작업 전극의 제조: 투명 전도성 산화물인 ITO 전극 상에 DC sputter 방식을 이용하여 산화텅스텐(WOx)으로 형성된 전기변색층을 300 nm 두께로 증착하고, 제1 전극과 전기변색층을 포함하는 작업전극을 제조하였다. Fabrication of Working Electrode: An electrochromic layer formed of tungsten oxide (WO x ) was deposited to a thickness of 300 nm on a transparent conductive oxide ITO electrode using a DC sputter method, and a working electrode including a first electrode and an electrochromic layer .
상대전극의 제조: 투명 전도성 산화물인 ITO 전극 상에 DC sputter 방식을 이용하여 질화구리(CuNx)를 포함하는 형성된 이온저장층을 30 nm 두께로 증착하고, 제2 전극과 이온저장층을 포함하는 작업전극을 제조하였다. Preparation of counter electrode: A formed ion storage layer containing copper nitride (CuN x ) was deposited to a thickness of 30 nm on a transparent conductive oxide ITO electrode using a DC sputter method, and a second electrode and an ion storage layer A working electrode was prepared.
비교예Comparative Example 1 One
이온저장층으로 100 nm 두께의 LiNiOx 층이 사용된 것을 제외하고, 상기 실시예와 마찬가지로, 서로 다른 ITO 전극 상에 DC sputter 방식을 이용하여 전기변색층 및 이온저장층을 마련하였다.An electrochromic layer and an ion storage layer were formed on different ITO electrodes using a DC sputtering method, except that a LiNiOx layer having a thickness of 100 nm was used as the ion storage layer.
항목Measure
Item
(Ω/□)TCO surface resistance
(Ω / □)
(mC)Charge quantity
(mC)
Col. / Ble.Time (s)
Col. / Ble.
(mC)Charge quantity
(mC)
Col. / Ble.Time (s)
Col. / Ble.
△T: 각 전극의 착색 및 탈색시 투과율 차이
Time(s) Col. : 전극이 탈색(bleaching) 상태에서 착색(coloring) 상태로 전환되는데 소요되는 시간. 완전 착색 상태의 투과율 대비 80% 투과율을 갖는 데까지 소요되는 시간으로 측정될 수 있다.
Time(s) Ble. : 전극이 착색(coloring) 상태에서 탈색(bleaching) 상태로 전환되는데 소요되는 시간. 완전 탈색 상태의 투과율 대비 80% 투과율을 갖는 데까지 소요되는 시간으로 측정될 수 있다.TCO surface resistance: sheet resistance value of ITO electrode
ΔT: Difference in transmittance between coloring and decoloring of each electrode
Time (s) Col. : The time it takes for the electrode to change from bleaching to coloring. Can be measured as the time taken to have an 80% transmittance versus a completely colored state.
Time (s) Ble. : The time it takes for the electrode to change from a coloring to a bleaching state. Can be measured as the time taken to have an 80% transmittance versus a completely discolored state.
상기 표 1에서와 같이, 본 출원의 상대전극에 포함된 이온저장층은 비교예의 이온저장층과 달리, 투과도 변화가 없는 것을 확인할 수 있다. 이는 비교예 이온저장층에 포함된 리튬니켈산화물의 경우 인가되는 전압에 따라 착색 및 탈색이 일어나는 반면, 실시예 이온저장층에 포함된 질화구리는 착색 및 탈색이 일어나지 않음을 의미한다. As shown in Table 1, unlike the ion storage layer of the comparative example, the ion storage layer included in the counter electrode of the present application shows no change in transmittance. This means that the coloring and decolorization of the lithium nickel oxide included in the comparative example ion storage layer occurs depending on the applied voltage, whereas the copper nitride contained in the ion storage layer of the embodiment does not cause discoloration and discoloration.
실험례Experimental Example 2: 풀-셀(Full-Cell)의 광학 특성 및 구동 특성 측정 2: Measurement of optical characteristics and driving characteristics of full-cell
상기 실시예 및 비교예에서 각각 제조된 작업전극과 상대전극을, PC(propylene carbonate)와 LiClO4의 혼합물로부터 제조된 겔 폴리머 전해질을 매개로 합착하고, 전기변색소자를 제조하였다. 제조된 전기변색소자에 대하여, 실험례 1과 동일한 장치를 이용하여 광학 및 구동 특성을 측정하였다. 그 결과는 하기 표 2와 같다.The working electrode and the counter electrode prepared in each of the above Examples and Comparative Examples were cemented through a gel polymer electrolyte prepared from a mixture of PC (propylene carbonate) and LiClO 4 to prepare an electrochromic device. Optical and drive characteristics of the electrochromic device were measured using the same apparatus as in Experiment 1. The results are shown in Table 2 below.
Time(s)Coloring
Time (s)
Time(s)Bleaching
Time (s)
Bleaching Time(s): 전기변색층이 착색(coloring) 상태에서 탈색(bleaching)될 경우 소요되는 시간. 완전 탈색 상태의 투과율 대비 80% 투과율을 갖는 데까지 소요되는 시간으로 측정될 수 있다.
Coloring Time(s): 전기변색층이 탈색(bleaching) 상태에서 착색(coloring)될 경우, 소요되는 시간. 완전 착색 상태의 투과율 대비 80% 투과율을 갖는 데까지 소요되는 시간으로 측정될 수 있다.ΔT: Difference in transmittance between coloring and decolorization of all devices
Bleaching Time (s): The time required when the electrochromic layer is bleached in the coloring state. Can be measured as the time taken to have an 80% transmittance versus a completely discolored state.
Coloring Time (s): The time required when the electrochromic layer is colored in the bleaching state. Can be measured as the time taken to have an 80% transmittance versus a completely colored state.
상기 표 2과 같이, 작업전극과 상대전극으로 구성된 전기변색소자 전체의 전하량은 비교예의 그것이 더 큰 것을 확인할 수 있다. 그러나, 전하량에 대한 투과도 변화로 나타낼 수 있는 변색효율(coloration efficiency=△T/전하량)의 경우, 비교예 소자 대비 실시예의 소자가 월등히 높은 것을 확인할 수 있다. 나아가, 실시예의 소자는 비교예 대비 50% 이상 단축된 스위칭 타임을 갖는 것을 확인할 수 있다.As shown in Table 2, it can be seen that the charge amount of the entire electrochromic device composed of the working electrode and the counter electrode is larger in the comparative example. However, in the case of the discoloration efficiency (coloration efficiency = DELTA T / charge amount) which can be represented by the change in the transmittance with respect to the charge amount, it can be confirmed that the elements of the embodiment are much higher than those of the comparative example. Further, it is confirmed that the device of the embodiment has a switching time shortened by 50% or more as compared with the comparative example.
Claims (19)
Wherein the electrochromic layer comprises tungsten oxide (WO x ), and the ion storage layer is made of copper nitride (CuN) or a mixture thereof. The electrochromic device of claim 1, x ). < / RTI >
The electrochromic device according to claim 1, wherein the copper nitride (CuN x ) satisfies a mass ratio of 0.05? N / Cu? 0.20.
The electrochromic device according to claim 1, wherein the ion storage layer has a resistance of 1,000 ohm / sq or less.
The electrochromic device according to claim 1, wherein the ion storage layer has a thickness in a range of 10 nm to 150 nm and a refractive index in a range of 2.0 to 3.5 with respect to visible light.
The electrochromic device according to claim 2, wherein a transmittance of the ion storage layer to visible light ranges from 60% to 80%.
The electrochromic device according to claim 1, wherein the electrochromic layer has a thickness of 50 nm to 400 nm.
The electrochromic device according to claim 1, wherein the electrochromic device layer has a transmittance of 10% to 50% with respect to visible light upon coloring and a transmittance of 45% to 85% with respect to visible light upon decolorization.
The electrochromic device according to claim 1, wherein the electrolyte layer has a thickness of 30 to 200 占 퐉, and a light transmittance to visible light ranges from 70% to 95%.
The electrochromic device according to claim 1, wherein the electrolyte layer comprises any one of a liquid electrolyte, a gel-type polymer electrolyte, and an inorganic solid electrolyte.
The electrochromic device according to claim 9, wherein the electrolyte is an inorganic solid electrolyte containing LiPON or Ta 2 O 5 .
The electrochromic device according to claim 9, wherein the electrolyte is a gel type polymer electrolyte formed from a cured product of a mixture containing a carbonate compound and a lithium compound,
The method of claim 11, wherein the carbonate compound is at least one compound selected from the group consisting of propylene carbonate (EC), ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethylmethyl carbonate Electrochromic device.
The method of claim 11, wherein the lithium compound is LiF, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiClO 3, LiAsF 6, LiSbF 6, LiAl0 4, LiAlCl 4, LiNO 3, LiN (CN) 2, LiPF 6, Li (CF 3) 2 PF 4 , Li (CF 3) 3 PF 3, Li (CF 3) 4 PF 2, Li (CF 3) 5 PF, Li (CF 3) 6 P, LiSO 3 CF 3, LiSO 3 Wherein the electrochromic device is at least one selected from the group consisting of C 4 F 9 , LiSO 3 (CF 2 ) 7 CF 3 , and LiN (SO 2 CF 3 ) 2 .
The method according to claim 1, wherein the electrode layer is formed of a material selected from the group consisting of indium tin oxide (ITO), fluoro-doped tin oxide (FTO), aluminum oxide doped zinc oxide (AZO), antimony doped tin oxide (ATO) At least one transparent conductive compound selected from the group consisting of Indium-doped Zinc Oxide (ITO), Niobium-doped Titanium Oxide (NTO), ZnO, Oxide / Metal / Oxide (OMO) Conductive polymer; Silver nanowires; And a metal mesh. The electrochromic device according to claim 1,
15. The electrochromic device according to claim 14, wherein the electrode layer has a thickness in the range of 1 nm to 1 占 퐉 and a transmittance to visible light ranges from 70% to 95%.
The electrochromic device according to claim 1, wherein the electrochromic device further comprises a power source, and the absolute value of the coloring potential and decoloring potential of the electrochromic device is 2 V or less.
다른 하나의 전극층 상에 텅스텐산화물층(WOx)을 마련하는 단계를 포함하는 전기변색소자의 제조방법.
Providing a copper nitride (CuN x ) layer having a copper / nitrogen mass ratio in the range of 0.05? N / Cu? 0.20 on one electrode layer; And
And forming a tungsten oxide layer (WO x ) on the other electrode layer.
The method of claim 17, wherein the layer of copper nitride (CuN x ) or the layer of tungsten oxide (WO x ) is deposited by a method selected from the group consisting of deposition, spin coating, dip coating, screen printing, gravure coating, a sol-gel method, or a slot die coating method.
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