KR101945434B1 - Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer - Google Patents
Self-powering electrochromic devices containing small molecule organic ligand-metal oxide layer Download PDFInfo
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- KR101945434B1 KR101945434B1 KR1020160158871A KR20160158871A KR101945434B1 KR 101945434 B1 KR101945434 B1 KR 101945434B1 KR 1020160158871 A KR1020160158871 A KR 1020160158871A KR 20160158871 A KR20160158871 A KR 20160158871A KR 101945434 B1 KR101945434 B1 KR 101945434B1
- Authority
- KR
- South Korea
- Prior art keywords
- layer
- acid
- hydroxy
- metal oxide
- ligand
- Prior art date
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 34
- 150000003384 small molecules Chemical class 0.000 title 1
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 37
- 239000003792 electrolyte Substances 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- -1 Diphenylamino Chemical group 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- DOUMFZQKYFQNTF-WUTVXBCWSA-N (R)-rosmarinic acid Chemical compound C([C@H](C(=O)O)OC(=O)\C=C\C=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-WUTVXBCWSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 6
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 229960004889 salicylic acid Drugs 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 6
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 claims description 5
- NJESAXZANHETJV-UHFFFAOYSA-N 4-methylsalicylic acid Chemical compound CC1=CC=C(C(O)=O)C(O)=C1 NJESAXZANHETJV-UHFFFAOYSA-N 0.000 claims description 5
- 229960004909 aminosalicylic acid Drugs 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- DLGBEGBHXSAQOC-UHFFFAOYSA-N 2-hydroxy-5-methylbenzoic acid Chemical compound CC1=CC=C(O)C(C(O)=O)=C1 DLGBEGBHXSAQOC-UHFFFAOYSA-N 0.000 claims description 4
- RJOWHWZRBQBAMZ-UHFFFAOYSA-N 2-hydroxy-5-pyrrol-1-ylbenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(N2C=CC=C2)=C1 RJOWHWZRBQBAMZ-UHFFFAOYSA-N 0.000 claims description 4
- QFBRTAZCGKXPJK-UHFFFAOYSA-N 4-chloro-6,7-dihydro-5h-cyclopenta[d]pyrimidine Chemical compound ClC1=NC=NC2=C1CCC2 QFBRTAZCGKXPJK-UHFFFAOYSA-N 0.000 claims description 4
- ZZAFFYPNLYCDEP-HNNXBMFYSA-N Rosmarinsaeure Natural products OC(=O)[C@H](Cc1cccc(O)c1O)OC(=O)C=Cc2ccc(O)c(O)c2 ZZAFFYPNLYCDEP-HNNXBMFYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- ZUCRGHABDDWQPY-UHFFFAOYSA-N pyrazine-2,3-dicarboxylic acid Chemical compound OC(=O)C1=NC=CN=C1C(O)=O ZUCRGHABDDWQPY-UHFFFAOYSA-N 0.000 claims description 4
- DOUMFZQKYFQNTF-MRXNPFEDSA-N rosemarinic acid Natural products C([C@H](C(=O)O)OC(=O)C=CC=1C=C(O)C(O)=CC=1)C1=CC=C(O)C(O)=C1 DOUMFZQKYFQNTF-MRXNPFEDSA-N 0.000 claims description 4
- TVHVQJFBWRLYOD-UHFFFAOYSA-N rosmarinic acid Natural products OC(=O)C(Cc1ccc(O)c(O)c1)OC(=Cc2ccc(O)c(O)c2)C=O TVHVQJFBWRLYOD-UHFFFAOYSA-N 0.000 claims description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 4
- XGAYQDWZIPRBPF-UHFFFAOYSA-N 2-hydroxy-3-propan-2-ylbenzoic acid Chemical compound CC(C)C1=CC=CC(C(O)=O)=C1O XGAYQDWZIPRBPF-UHFFFAOYSA-N 0.000 claims description 3
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 3
- RVGATDHHYVSTQG-UHFFFAOYSA-N 3-hydroxy-2-methylquinoline-4-carboxylic acid Chemical compound C1=CC=C2C(C(O)=O)=C(O)C(C)=NC2=C1 RVGATDHHYVSTQG-UHFFFAOYSA-N 0.000 claims description 3
- NMOWGWOAPRKWIR-UHFFFAOYSA-N 3-oxo-4h-quinoxaline-2-carboxylic acid Chemical compound C1=CC=C2NC(=O)C(C(=O)O)=NC2=C1 NMOWGWOAPRKWIR-UHFFFAOYSA-N 0.000 claims description 3
- 229910015892 BF 4 Inorganic materials 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- GXAMYUGOODKVRM-UHFFFAOYSA-N Flurecol Chemical compound C1=CC=C2C(C(=O)O)(O)C3=CC=CC=C3C2=C1 GXAMYUGOODKVRM-UHFFFAOYSA-N 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 3
- 229910021115 PF 6 Inorganic materials 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 3
- 150000004693 imidazolium salts Chemical class 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 150000002596 lactones Chemical class 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 3
- 125000005504 styryl group Chemical group 0.000 claims description 3
- XRIHTJYXIHOBDQ-UHFFFAOYSA-N 6-methyl-2-oxo-1h-pyridine-3-carboxylic acid Chemical compound CC1=CC=C(C(O)=O)C(=O)N1 XRIHTJYXIHOBDQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011245 gel electrolyte Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims 2
- 239000010948 rhodium Substances 0.000 claims 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 2
- IAEWPBXIUAUDOC-UHFFFAOYSA-N C1(=CC=CC=C1)N(C1=CC=C(C=C1)C1=CC(=C(C=C1)O)C(=O)O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)C1=CC(=C(C=C1)O)C(=O)O)C1=CC=CC=C1 IAEWPBXIUAUDOC-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
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- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
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- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 3
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Abstract
본 발명은 리간드-금속산화물층을 포함하는 자기구동 전기변색소자를 개시한다.
본 발명에 따르는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자는 리간드가 흡착된 금속산화물층이 적층된 제1투명전극층을 구비한 제1투명기판과, 상기 제1투명기판과 대향하여 전해질을 개재시키며 제1투명기판을 향한 면에 전기변색층을 적층한 제2투명기판 및 제1투명전극층과 전기변색층을 전기적으로 연결시키거나 차단하는 스위칭부를 포함하는데, 이에 의할 때, 향상된 투명도를 제공하고 외부의 광원에 의하여 자체적으로 전기변색이 가능하여 스마트 윈도우의 품위를 향상시킬 수 있는, 동시에 제조단가를 낮추고, 장기안정성을 높일 수 있다.The present invention discloses a self-driving electrochromic device comprising a ligand-metal oxide layer.
A magnetic driving electrochromic device comprising a ligand-metal oxide layer according to the present invention comprises: a first transparent substrate having a first transparent electrode layer on which a ligand-adsorbed metal oxide layer is laminated; and a second transparent electrode layer A second transparent substrate on which an electrochromic layer is laminated on a surface facing the first transparent substrate, and a switching unit electrically connecting or disconnecting the electrochromic layer with the first transparent electrode layer. In this case, And it is possible to perform electrochromic coloring by an external light source, thereby improving the quality of the smart window, lowering the manufacturing cost, and improving the long-term stability.
Description
본 발명은 리간드-금속산화물층을 포함하는 자기구동 전기변색소자에 관한 것으로서, 더욱 상세하게는 향상된 투명도를 제공하고 외부의 광원에 의하여 자체적으로 전기변색이 가능하여 스마트 윈도우의 품위를 향상시킬 수 있는, 동시에 제조단가를 낮추고, 장기안정성을 높이는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자에 관한 것이다.The present invention relates to a self-driving electrochromic device comprising a ligand-metal oxide layer, and more particularly, to a self-driving electrochromic device including a ligand-metal oxide layer, which can improve transparency and enable electrochemical coloring by an external light source, , And a ligand-metal oxide layer that simultaneously lowers the manufacturing cost and improves long-term stability.
최근 에너지 효율을 향상시키고 감성과 기능성을 동시에 만족시킬 수 있는 스마트 윈도우(Smart window) 기술이 큰 주목을 받고 있다.Recently, a smart window technology that can enhance energy efficiency and satisfy both sensibility and functionality has received great attention.
스마트 윈도우란 외부에서 유입되는 빛의 양을 조절하여 에너지 손실을 줄이고 소비자에게는 쾌적한 환경을 제공할 수 있는 능동 제어 기술을 의미하며 수송, 정보 디스플레이, 건축 등 다양한 산업 분야에 공통적으로 적용될 수 있는 기반 기술이라 할 수 있다.Smart window means active control technology that can reduce the energy loss by adjusting the amount of light coming from the outside and provide a comfortable environment to the consumers. It can be applied to various fields such as transportation, information display, .
이러한 스마트 윈도우는 구동 방식에 따라 헤드업 디스플레이 방식(Head up display, HUD), 변색 방식(Chromic display, CD), 분극 입자 방식(Suspended particle display, SPD), 고분자/액정 복합필름 방식(Polymer/Liquid crystal composites film)으로 분류될 수 있다.These smart windows can be classified into a head up display (HUD), a chromatic display (CD), a suspended particle display (SPD), a polymer / crystal composites film).
여기서, 변색 방식 중 전기변색(electrochromism)은 외부에서 전압이 가해졌을 때 빛의 투과율이나 색을 변화시키는 현상을 의미한다. 이와 같은 전기 변색소자의 특징으로는 작동 전압이 1.5V 이하로 적고, 광변색 효율이 크며, 개방(open circuit) 상태에서도 메모리 효과를 가지고 있기 때문에 전압을 계속 가해줄 필요가 없다는 점이다. Here, electrochromism in the discoloration method means a phenomenon in which the transmittance or color of light is changed when an external voltage is applied. The characteristics of such an electrochromic device are that the operating voltage is less than 1.5 V, the photochromic efficiency is high, and the memory effect is achieved even in the open circuit state.
도 6은 종래 전기변색 소자의 내부 구조를 나타낸 것으로, 작업전극으로 투명전도체 위에 WO3 전기변색층이 있고, 상대전극으로 투명전도체 위에 이온저장층이 위치하며, 이들 사이에 전해질이 개재되어 있는 전기화학적 구조를 가진다.FIG. 6 shows an internal structure of a conventional electrochromic device, in which a WO 3 electrochromic layer is disposed on a transparent conductor as a working electrode, an ion storage layer is disposed on a transparent conductor as a counter electrode, It has a chemical structure.
일반적으로 상기 작업전극에 있는 전기변색층으로서는 환원반응(cathodic reaction)이 일어날 때 착색(coloration)이 일어나고, 산화반응(anodic reaction)이 일어날 때 탈색(bleaching)이 일어나는 물질을 사용할 수 있다.In general, the electrochromic layer in the working electrode may be a material that undergoes coloration when a cathodic reaction occurs and causes bleaching when an anodic reaction occurs.
또한, 상대전극의 이온저장층의 경우 환원반응이나 산화반응에 관계없이 단순히 이온을 저장하거나 내보내는 역할을 하고, 다른 한편으로 이온저장층은 작업전극과 반대로 산화반응일 때 착색되고 환원반응일 때 탈색되는 물질을 사용할 수도 있으며, 이런 경우 작업전극과 함께 착색되거나 탈색이 동시에 일어남으로 소자의 명암 특성을 향상시킬 수 있는데, 이러한 물질의 대표적인 예로 니켈산화물(NiOs), 이리듐산화물(IrOs), 바나듐산화물(VOs) 등을 들 수 있다.In addition, the ion storage layer of the counter electrode plays a role of simply storing or discharging ions irrespective of a reduction reaction or an oxidation reaction. On the other hand, the ion storage layer is colored when the reaction is opposite to the working electrode, (NiOs), iridium oxides (IrOs), vanadium oxides (IrO2), and vanadium oxides (IrO2) can be used. In this case, coloring or discoloration occurs simultaneously with the working electrode, VOs) and the like.
이렇듯이, 전기변색소자는 LED, 액정 표시 소자 등 다른 여타의 디스플레이소자보다 작동 전압(1.5V 이하)이 매우 낮기 때문에 태양전지같은 저전압 전력원과 하이브리드 타입으로 개발되기도 하는데, 미국특허 5,384,653호 및 5,377,037호의 경우 p-n 접합형 태양전지(또는 Si 태양전지)를 이용하여 전기변색 소자와 하이브리드 형태로 제작된바 있다. As described above, since the electrochromic device has a very low operating voltage (less than 1.5 V) than other display devices such as LEDs and liquid crystal display devices, it may be developed as a hybrid type with a low voltage power source such as a solar cell. U.S. Patent Nos. 5,384,653 and 5,377,037 The solar cell has been fabricated in a hybrid form with an electrochromic device using a pn junction solar cell (or Si solar cell).
그러나 Si이 불투명하기 때문에 반투명하게 만들기 위해 적어도 100nm 두께 이하로 태양전지를 제작하여야 하므로 제작이 쉽지 않을 뿐만 아니라 태양전지의 단락을 용이하게 하고, 제조원가를 높이는 문제를 가지고 있으며, 염료감응형 태양전지는 투과성이 낮은 문제를 여전히 가지고 있었다. However, since Si is opaque, it is necessary to fabricate a solar cell with a thickness of at least 100 nm in order to make it translucent, so that it is not easy to manufacture, and it has a problem of facilitating the short circuit of the solar cell and raising the manufacturing cost. But still had low permeability problems.
본 발명이 해결하고자 하는 기술적 과제는 향상된 투명도를 제공하고 외부의 광원에 의하여 자체적으로 전기변색이 가능하여 스마트 윈도우의 품위를 향상시킬 수 있는 동시에, 제조단가를 낮추고, 장기안정성을 높이는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자를 제공하는 것이다.Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and it is an object of the present invention to provide a ligand-metal oxide Layer is formed on the surface of the electrochromic device.
본 발명은 상술한 기술적 과제를 해결하기 위하여, 리간드가 흡착된 금속산화물층이 적층된 제1투명전극층을 구비한 제1투명기판과, 상기 제1투명기판과 대향하여 전해질을 개재시키며 제1투명기판을 향한 면에 전기변색층을 적층한 제2투명기판 및 제1투명전극층과 전기변색층을 전기적으로 연결시키거나 차단하는 스위칭부를 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자를 제공한다.SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned technical problems, and it is an object of the present invention to provide an organic EL display device, which comprises a first transparent substrate having a first transparent electrode layer on which a metal oxide layer adsorbed with a ligand is laminated, A second transparent substrate on which an electrochromic layer is laminated on a surface facing the substrate, and a switching unit electrically connecting or disconnecting the first transparent electrode layer and the electrochromic layer. Thereby providing an electrochromic device.
본 발명의 일실시예에 의하면, 상기 리간드는 2,3-살리실산(2,3-Salicylic acid), 2,3-피라진디카복실산(2,3-Pyrazine dicarboxylic acid), 로즈마린산(Rosmarinic acid), 시트르산(Citric acid), 붕산(Boric acid), 3-메틸살리실산(3-Methylsalicylic acid), 4-메틸살리실산(4-Methyl salicylic acid), 5-메틸살리실산(5-Methyl salicylic acid), 4-아미노살리실산(4-Aminosalicylic acid), 2-히드록시니코틴산(2-Hydroxynicotinic acid), 3-히드록시피콜리닉산(3-Hydroxypicolinic acid), 2-히드록시-1-나프토산(2-Hydroxy-1-naphthoic acid), 3-히드록시-2-나프토산(3-Hydroxy-2-naphthoic acid), 3-히드록시-2-메틸-4-퀴놀린카복실산(3-Hydroxy-2-methyl-4-quinolinecarboxylic acid), 2-히드록시-3-이소프로필벤조산(2-Hydroxy-3-isopropylbenzoic acid), 2-히드록시-5-(1H-피롤-1-일)벤조산(2-Hydroxy-5-(1H-pyrrol-1-yl)benzoic acid), 2-히드록시-6-메틸피리딘-3-카복실산(2-Hydorxy-6-methylpyridine-3-carboxylic acid), 2-(4-히드록시페닐아조)벤조산(2-(4-Hydroxyphenylazo)benzoic acid), 1-히드록시-2-나프토산(1-Hydroxy-2-naphthoic acid), 4-히드록시-7-트리플루오로메틸-3-퀴놀린카복실산(4-Hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid), 3-히드록시-2-퀴녹살린카복실산(3-Hydroxy-2-quinoxaline carboxylic acid), 9-히드록시-9-플루오렌카복실산(9-Hydroxy-9-fluorene carboxylic acid), 4'-(디페닐아미노)-4-히드록시-[1,1'-비페닐]-3-카복실산(4'-(Diphenylamino)-4-hydroxy-[1,1'-biphenyl]-3-carboxylic acid) 또는 4-(4-(디페닐아미노)스티릴)-2-히드록시벤조산(4-(4-(Diphenylamino)styryl)-2-hydroxybenzoic acid)로부터 선택되는 적어도 하나일 수 있다.According to one embodiment of the present invention, the ligand is selected from the group consisting of 2,3-salicylic acid, 2,3-pyrazine dicarboxylic acid, rosmarinic acid, Citric acid, boric acid, 3-methylsalicylic acid, 4-methyl salicylic acid, 5-methyl salicylic acid, 4-amino salicylic acid, 2-hydroxy-1-naphthoic acid, 4-aminosalicylic acid, 2-hydroxynicotinic acid, 3-hydroxypicolinic acid, 3-Hydroxy-2-naphthoic acid, 3-Hydroxy-2-methyl-4-quinolinecarboxylic acid, 2-hydroxy-3-isopropylbenzoic acid, 2-hydroxy-5- (1H-pyrrole) -1-yl) benzoic acid, 2-Hydorxy-6-methylpyridine-3-carbo xylic acid, 2- (4-hydroxyphenylazo) benzoic acid, 1-hydroxy-2-naphthoic acid, Hydroxy-2-quinolinecarboxylic acid, 3-hydroxy-2-quinolinecarboxylic acid, 4-hydroxy- 9-Hydroxy-9-fluorene carboxylic acid, 4 '- (diphenylamino) -4-hydroxy- [1,1'-biphenyl] -3-carboxylic acid 4 - (diphenylamino) -4-hydroxy- [1,1'-biphenyl] -3-carboxylic acid or 4- (4- (diphenylamino) styryl) -2-hydroxybenzoic acid (4- - (diphenylamino) styryl) -2-hydroxybenzoic acid).
본 발명의 다른 실시예에 의하면, 상기 리간드는 히드록시기가 치환된 벤젠구조를 포함하는 화합물로, 히드록시기의 파라, 메타, 오르토위치에 전자주개작용기가 치환된 것일 수 있다.According to another embodiment of the present invention, the ligand may be a compound containing a benzene structure in which a hydroxy group is substituted, in which an electron-former manipulation vessel is substituted for the para, meta, and ortho positions of the hydroxy group.
본 발명의 또 다른 실시예에 의하면, 상기 전자주개작용기의 위치는 파라, 오르토, 메타순으로 전기변색 정도가 증가되는 것일 수 있다.According to another embodiment of the present invention, the position of the electron mosaic container may be one in which the degree of electrochromism is increased in the order of para, ortho, and meta.
본 발명의 또 다른 실시예에 의하면, 상기 전해질은 브로마이드계화합물을 포함하는 것일 수 있다.According to another embodiment of the present invention, the electrolyte may include a bromide-based compound.
본 발명의 또 다른 실시예에 의하면, 상기 브로마이드계화합물은 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, 4급 암모늄염, 이미다졸륨염 및 피리디늄염으로 이루어지는 군으로부터 선택되는 적어도 하나일 수 있다.According to another embodiment of the present invention, the bromide-based compound may be at least one selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salt, imidazolium salt and pyridinium salt.
본 발명의 또 다른 실시예에 의하면, 상기 전해질은 리튬염으로서 ClO4, BF4, PF6, OTf(trifluoromethanesulfonate), TFSI(CF3SO2)2N 또는 B(CN)4 작용기를 포함할 수 있다.According to a further embodiment of the invention, the electrolyte is a lithium salt, ClO 4, BF 4, PF 6 , OTf (trifluoromethanesulfonate), TFSI (CF 3 SO 2) 2 N , or B can comprise a (CN) 4 functional groups have.
본 발명의 또 다른 실시예에 의하면, 상기 리튬염은 산화환원재로 Co(III)/Co(II) 또는 Fe/Fe+을 포함하는 것일 수 있다.According to another embodiment of the present invention, the lithium salt may be one containing Co (III) / Co (II) or Fe / Fe + as a redox material.
본 발명의 또 다른 실시예에 의하면, 상기 브로마이드계화합물은 리튬염을 더 포함하는 것일 수 있다.According to another embodiment of the present invention, the bromide-based compound may further include a lithium salt.
본 발명의 또 다른 실시예에 의하면, 상기 전해질은 나이트라일계, 락톤계, 설폰계, 카보네이트계, 피롤리돈계 및 아마이드계로 이루어지는 유기용매군으로부터 선택되는 적어도 하나를 용매로 포함할 수 있다.According to another embodiment of the present invention, the electrolyte may include at least one solvent selected from the group consisting of nitriles, lactones, sulfones, carbonates, pyrrolidones and amides.
본 발명의 또 다른 실시예에 의하면, 상기 전해질은 이미다졸리움, 피롤리디움, 피리디니움으로 이루어지는 이온성 액체계 전해질군으로부터 선택되는 적어도 하나일 수 있다..According to another embodiment of the present invention, the electrolyte may be at least one selected from the group consisting of imidazolium, pyrrolidinium, and pyridinium ionic liquid-based electrolytes.
본 발명의 또 다른 실시예에 의하면, 상기 전해질은 금속산화물을 평균입균이 10 내지 500㎜인 나노입자를 포함하는 겔형 전해질일 수 있다.According to another embodiment of the present invention, the electrolyte may be a gel electrolyte including nanoparticles having an average diameter of 10 to 500 mm.
본 발명의 또 다른 실시예에 의하면, 상기 전기변색층은 산화텅스텐(WO3), 산화몰리브덴(MoO3), 산화나이오븀(Nb2O5), 산화바나듐(V2O5), 산화티탄(TiO2), 수산화이리듐, 수산화니켈, 산화로듐 및 산화코발트로 이루어진 군에서 선택된 적어도 하나일 수 있다.According to another embodiment of the present invention, the electrochromic layer may include at least one of tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), niobium oxide (Nb 2 O 5 ), vanadium oxide (V 2 O 5 ) (TiO 2 ), iridium hydroxide, nickel hydroxide, rhodium oxide and cobalt oxide.
본 발명의 또 다른 실시예에 의하면, 상기 제2투명기판과 전기변색층과의 사이에 제2투명전극층을 더 구비하여 일단부에는 제2전극단자층을 구비하고, 타단부에는 제1전극대향부를 구비하는 것일 수 있다.According to another embodiment of the present invention, a second transparent electrode layer is further provided between the second transparent substrate and the electrochromic layer, and a second electrode terminal layer is provided at one end, and a second electrode terminal layer is provided at the other end, Or the like.
본 발명의 또 다른 실시예에 의하면, 상기 제2전극단자층에서 연장되어 전기변색층의 하부에 배치되는 복수개의 제2보조단자층을 구비하는 것일 수 있다.According to another embodiment of the present invention, a plurality of second auxiliary terminal layers extending from the second electrode terminal layer and disposed under the electrochromic layer may be provided.
본 발명의 또 다른 실시예에 의하면, 상기 제2보조단자층은 10 내지 500㎛의 선폭을 가지는 것일 수 있다.According to another embodiment of the present invention, the second auxiliary terminal layer may have a line width of 10 to 500 m.
본 발명의 또 다른 실시예에 의하면, 상기 제1투명전극층에는 상기 제1전극대향부에 대향되는 부분에 제1전극단자층을 적층하는 것일 수 있다.According to another embodiment of the present invention, the first electrode terminal layer may be formed on the first transparent electrode layer in a portion opposed to the first electrode facing portion.
본 발명의 또 다른 실시예에 의하면, 상기 제1전극단자층에서 연장되어 금속산화물층의 하부에 배치되는 복수개의 제1보조단자층을 구비하는 것일 수 있다.According to another embodiment of the present invention, a plurality of first auxiliary terminal layers extending from the first electrode terminal layer and disposed below the metal oxide layer may be provided.
본 발명의 또 다른 실시예에 의하면, 상기 제1보조단자층은 10 내지 500 ㎛의 선폭을 가지는 것일 수 있다.According to another embodiment of the present invention, the first auxiliary terminal layer may have a line width of 10 to 500 탆.
본 발명에 따르는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자에 의하면, 향상된 투명도를 제공하고 외부의 광원에 의하여 자체적으로 전기변색이 가능하여 스마트 윈도우의 품위를 향상시킬 수 있는, 동시에 제조단가를 낮추고, 장기안정성을 높이는 효과를 발휘할 수 있다.According to the self-driving electrochromic device including the ligand-metal oxide layer according to the present invention, it is possible to provide an improved transparency and to improve the quality of a smart window by enabling electrochemical coloring by an external light source, And the long-term stability can be enhanced.
도 1은 본 발명의 전기변색소자의 구성을 개념적으로 나타낸 그림이고,
도 2는 본 발명의 제1,2투명기판에 구현된 전극단자층과 보조단자층의 일예를 사시적으로 분리하여 보여주는 도면이며,
도 3은 본 발명에 따르는 여러 실시예의 음극계전극과 비교예의 음극계전극의 투과율을 보여주는 그래프이고,
도 4는 본 발명에 따르는 여러 실시예의 착색후 투과도와 비교예의 착색후 투과도를 나타낸 그래프이며,
도 5은 본 발명에 따르는 여러 실시예의 탈색후 투과도와 비교예의 탈색후 투과도를 보여주는 그래프이며,
도 6은 종래 전기변색소자의 특성을 모식적으로 나타낸 그림이다.1 is a conceptual illustration of the configuration of the electrochromic device of the present invention,
2 is a perspective view showing an example of an electrode terminal layer and an auxiliary terminal layer implemented in the first and second transparent substrates of the present invention,
3 is a graph showing the transmittance of the negative electrode of the various embodiments and the negative electrode of the comparative example according to the present invention,
4 is a graph showing transmittance after coloring of various examples according to the present invention and transmittance after coloring of a comparative example,
5 is a graph showing the post-decoloring transmittance and the post-decoloring transmittance of the comparative example of various embodiments according to the present invention,
6 is a diagram schematically showing characteristics of a conventional electrochromic device.
이하에서는 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용되는 기술적 용어는 단지 특정한 실시 예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아님을 유의해야 한다. 또한, 본 발명에서 사용되는 기술적 용어는 본 발명에서 특별히 다른 의미로 정의되지 않는 한, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 의미로 해석되어야 하며, 과도하게 포괄적인 의미로 해석되거나, 과도하게 축소된 의미로 해석되지 않아야 한다. 또한, 본 발명에서 사용되는 기술적인 용어가 본 발명의 사상을 정확하게 표현하지 못하는 잘못된 기술적 용어일 때에는, 당업자가 올바르게 이해할 수 있는 기술적 용어로 대체되어 이해되어야 할 것이다. 또한, 본 발명에서 사용되는 일반적인 용어는 사전에 정의되어 있는 바에 따라, 또는 전후 문맥상에 따라 해석되어야 하며, 과도하게 축소된 의미로 해석되지 않아야 한다.It is noted that the technical terms used in the present invention are used only to describe specific embodiments and are not intended to limit the present invention. In addition, the technical terms used in the present invention should be construed in a sense generally understood by a person having ordinary skill in the art to which the present invention belongs, unless otherwise defined in the present invention, Should not be construed to mean, or be interpreted in an excessively reduced sense. In addition, when a technical term used in the present invention is an erroneous technical term that does not accurately express the concept of the present invention, it should be understood that technical terms can be understood by those skilled in the art. In addition, the general terms used in the present invention should be interpreted according to a predefined or prior context, and should not be construed as being excessively reduced.
또한, 본 발명에서 사용되는 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한 복수의 표현을 포함한다. 본 발명에서, "구성된다" 또는 "포함한다" 등의 용어는 발명에 기재된 여러 구성 요소들, 또는 여러 단계를 반드시 모두 포함하는 것으로 해석되지 않아야 하며, 그 중 일부 구성 요소들 또는 일부 단계들은 포함되지 않을 수도 있고, 또는 추가적인 구성 요소 또는 단계들을 더 포함할 수 있는 것으로 해석되어야 한다.Furthermore, the singular expressions used in the present invention include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "comprising" or "comprising" and the like should not be construed as encompassing various elements or various steps of the invention, Or may further include additional components or steps.
도 1은 본 발명의 전기변색소자의 구성을 단면적으로 나타낸 그림이고, 도 2는 본 발명의 제1,2투명기판에 구현된 전극단자층과 보조단자층의 일예를 사시적으로 분리하여 보여주는 도면이며, 도 3은 본 발명에 따르는 여러 실시예의 음극계전극과 비교예의 음극계전극의 투과율을 보여주는 그래프이고, 도 4는 본 발명에 따르는 여러 실시예의 착색후 투과도와 비교예의 착색후 투과도를 나타낸 그래프이며, 도 5은 본 발명에 따르는 여러 실시예의 탈색후 투과도와 비교예의 탈색후 투과도를 보여주는 그래프인데, 이를 참고하여 설명한다.FIG. 1 is a cross-sectional view showing the configuration of the electrochromic device of the present invention. FIG. 2 is a cross-sectional view illustrating an example of an electrode terminal layer and an auxiliary terminal layer implemented in the first and second transparent substrates of the present invention FIG. 3 is a graph showing the transmittance of the negative electrode of the various embodiments of the present invention and the negative electrode of the comparative example, FIG. 4 is a graph showing the transmittance after coloring of the various embodiments of the present invention and the transmittance after coloring of the comparative example FIG. 5 is a graph showing the post-decoloring transmittance and the post-decoloring transmittance of the comparative example according to various embodiments of the present invention.
본 발명에 따르는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자(1000)는 리간드(130)가 흡착된 금속산화물층(120)이 적층된 제1투명전극층(110)을 구비한 제1투명기판(100)과, 상기 제1투명기판과 대향하여 전해질(300)을 개재시키며 제1투명기판을 향한 면에 전기변색층(220)을 적층한 제2투명기판(200) 및 제1투명전극층과 전기변색층을 전기적으로 연결시키거나 차단하는 스위칭부(Sw)를 포함하는 특징이 있다.A magnetic
상기 리간드(130, ligand)는 착화합물에서 중심 금속 원자에 전자쌍을 제공하면서 배위 결합을 형성하는 원자나 원자단이라는 사전적 의미를 가지나, 본 발명에서는 상기 금속산화물층에서 전자주개 역할을 하는 화합물을 포함하는 것으로, 2,3-살리실산(2,3-Salicylic acid), 2,3-피라진디카복실산(2,3-Pyrazine dicarboxylic acid), 로즈마린산(Rosmarinic acid), 시트르산(Citric acid), 붕산(Boric acid), 3-메틸살리실산(3-Methylsalicylic acid), 4-메틸살리실산(4-Methyl salicylic acid), 5-메틸살리실산(5-Methyl salicylic acid), 4-아미노살리실산(4-Aminosalicylic acid), 2-히드록시니코틴산(2-Hydroxynicotinic acid), 3-히드록시피콜리닉산(3-Hydroxypicolinic acid), 2-히드록시-1-나프토산(2-Hydroxy-1-naphthoic acid), 3-히드록시-2-나프토산(3-Hydroxy-2-naphthoic acid), 3-히드록시-2-메틸-4-퀴놀린카복실산(3-Hydroxy-2-methyl-4-quinolinecarboxylic acid), 2-히드록시-3-이소프로필벤조산(2-Hydroxy-3-isopropylbenzoic acid), 2-히드록시-5-(1H-피롤-1-일)벤조산(2-Hydroxy-5-(1H-pyrrol-1-yl)benzoic acid), 2-히드록시-6-메틸피리딘-3-카복실산(2-Hydorxy-6-methylpyridine-3-carboxylic acid), 2-(4-히드록시페닐아조)벤조산(2-(4-Hydroxyphenylazo)benzoic acid), 1-히드록시-2-나프토산(1-Hydroxy-2-naphthoic acid), 4-히드록시-7-트리플루오로메틸-3-퀴놀린카복실산(4-Hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid), 3-히드록시-2-퀴녹살린카복실산(3-Hydroxy-2-quinoxaline carboxylic acid), 9-히드록시-9-플루오렌카복실산(9-Hydroxy-9-fluorene carboxylic acid), 4'-(디페닐아미노)-4-히드록시-[1,1'-비페닐]-3-카복실산(4'-(Diphenylamino)-4-hydroxy-[1,1'-biphenyl]-3-carboxylic acid) 또는 4-(4-(디페닐아미노)스티릴)-2-히드록시벤조산(4-(4-(Diphenylamino)styryl)-2-hydroxybenzoic acid)로부터 선택되는 적어도 하나인 것일 수 있다.The
이러한 리간드는 히드록시기(OH-)가 치환된 벤젠구조(benzene)를 포함하는 화합물로, 히드록시기의 파라(para), 메타(meta), 오르토(ortho) 위치에 전자주개작용기가 치환된 것이 전기변색이 효과적으로 잘 일어날 수 있다.This ligand is a compound containing a benzene structure in which a hydroxyl group (OH-) is substituted. The substitution of an electron-former reaction vessel at the para, meta, This can happen quite effectively.
아울러, 이 경우에 전자주개 작용기의 위치는 파라, 오르토, 메타순으로 전기변색 정도가 증가되어 착색이나 탈색이 효과적으로 일어날 수 있다.In addition, in this case, the position of the electron-donating functional group is increased in the order of para, ortho, and meta in order to effectively cause coloring or discoloration.
상기 제1투명기판(100)은 제1투명전극층(110)을 적층하고 있는 투명한 소재로 이루어진 판재로 평평한 것은 물론 일정 곡률을 가지고 휘어져(curved)있는 것일 수 있으며, 유리재는 물론 투명한 고분자재로, PET, PEN, PC, PP, PI 또는 TAC 등과 같은 소재가 필요에 따라 선택적으로 사용될 수 있다.The first
또한, 상기 제1투명전극층(110)은 수㎚ 에서 수㎛ 두께로 제1투명기판에 스퍼터나 화학기상증착방법으로 적층된 전극층으로, 인듐틴옥사이드(ITO), 플루오르틴옥사이드(FTO), ZnO-(Ga2O3 또는 Al2O3) 또는 SnO2-Sb2O3가 구비될 수 있다.In addition, the first
아울러, 상기 제1투명전극층에는 금속산화물층(120)이 통전성을 가지고, 리간드(130)의 흡착성과 내구성을 확보하기 위하여 구비되며, 이산화티탄(TiO2), 산화아연(ZnO), 산화주석(SnO2), 산화나이오븀(Nb2O5) 등을 사용할 수 있다.A
한편, 상기 제2투명기판(200)은 제1투명기판과 대향되게 배치되며, 그 내부에 전해질(300)을 개재시키고 전기변색층(220)을 적층하고 있고, 이러한 상기 제2투명기판은 투명한 소재로 이루어진 판재로 평평한 것은 물론 일정 곡률을 가지고 휘어져(curved)있는 것일 수 있으며, 유리재는 물론 투명한 고분자재로, PET, PEN, PC, PP, PI 또는 TAC 등과 같은 소재가 필요에 따라 선택적으로 사용될 수 있다.Meanwhile, the second
또한, 상기 제2투명기판(200)은 통전성을 확보하고, 더 나아가 경시적으로 발생할 수 있는 접촉저항(contact resistance)의 증가를 방지하기 위해 제2투명전극층(210)을 적층할 수 있어, 제1투명전극층(110)와 함께, 회로를 열거나 닫을 수 있는 스위칭부(Sw)와 연결되어 외부의 회로나 부하와 폐회로를 구성할 수 있는데, 제1투명전극층과 마찬가지로 수㎚ 에서 수㎛ 두께로 제1투명기판에 스퍼터나 화학기상증착방법으로 적층된 전극층으로, 인듐틴옥사이드(ITO), 플루오르틴옥사이드(FTO), ZnO-(Ga2O3 또는 Al2O3) 또는 SnO2-Sb2O3가 구비될 수 있다.In addition, the second
또한, 상기 스위칭부는 투명전극층과 직접 회로를 구성하면 접촉저항증가나 내구성이 감소되는 문제가 생길 수 있으므로, 별도의 전극단자를 구성할 수 있다.In addition, when the switching unit is integrated with the transparent electrode layer, a contact resistance increase and a durability may be reduced. Therefore, a separate electrode terminal can be formed.
예를 들어, 상기 제2투명기판과 전기변색층과의 사이에 제2투명전극층을 더 구비하여 일단부에는 제2전극단자층(210')을 구비하고, 타단부에는 제1전극대향부(212)를 구비하고, 상기 제1투명전극층에는 상기 제1전극대향부(212)에 대향되는 부분에 제1전극단자층(110')을 적층하여 제1,2전극단자층과 스위칭부로 회로를 구성할 수 있음은 물론, 경시적으로 발생할 수 있는 접촉저항의 증가를 방지하고, 안정적인 전압인가를 수행할 수 있다.For example, a second transparent electrode layer may be further provided between the second transparent substrate and the electrochromic layer, and a second electrode terminal layer 210 'may be provided at one end and a first electrode opposing portion And a first electrode terminal layer 110 'is laminated on a portion of the first transparent electrode layer opposite to the first
이러한 제1전극단자층(110')은 띠 형태의 제1투명전극층에서 안정적인 전압인가를 위해 대향하는 위치에 제1'전극단자층(110")을 배치하여 회로에 연결할 수 있으며, 마찬가지로 제2전극단자층(210') 역시 제2'전극단자층(210")을 구비하여 스위칭부와 회로를 구성할 수 있다.The first electrode terminal layer 110 'may be connected to a circuit by disposing a first electrode terminal layer 110' at a position opposite to the first electrode terminal layer 110 'in order to apply a stable voltage to the first transparent electrode layer in the form of a strip. The electrode terminal layer 210 'may also include a second' electrode terminal layer 210 'to form a circuit with the switching part.
더 나아가, 상기 제1,2투명전극층(110, 210)으로부터 전달되는 전자나 정공의 흐름을 효율적으로 하기 위하여 상기 제2전극단자층에서 연장되어 전기변색층의 하부에 배치되는 복수개의 제2보조단자층(214)을 구비하거나, 상기 제1전극단자층에서 연장되어 금속산화물층의 하부에 배치되는 복수개의 제1보조단자층(114)을 더 구비할 수 있다.In order to efficiently flow the electrons or holes from the first and second
상기 제1,2보조단자층(114, 214)에 의하여 전자나 정공의 안정적인 흐름을 유도하여 스위칭부와 연결되는 회로의 전압인가를 원활하게 수행할 수 있고, 전기변색소자는 산화나 환원시 투명한 특성을 디스플레이 어플레케이션에 적용하는 경우, 예컨대 창호로 사용하는 경우에 이용자에게 쾌적한 시인성을 제공할 수 있어야 하므로, 상기 제1,2보조단자층(114, 214)은 그 선폭(Wx, Wy)을 10 내지 500㎛로 할 수 있으며, 하한치 미만이면 선저항이 증가될 수 있으며, 상한치를 초과하면 투과율이 저감될 수 있고 시인성에 악영향을 미칠 수 있다.The first and second auxiliary
또한, 상술한 제1,2전극단자층(110', 210'), 제1,2보조단자층(114, 214)은 저항값이 작고 내구성이 보장될 수 있는 재료인 한 특별하게 한정할 것은 아니나, 실버분말(silver powder)을 용기용제, 솔더재와 배합하여 페이스트상으로 준비한 실버페이스트를 인쇄될 제1,2전극단자층, 제1,2보조전극단자층이 개구되도록 패턴된 스크린인쇄를 통하여 형성할 수 있어, 비용적으로, 시간적으로나 공정적으로 이익을 확보할 수 있다.The first and second electrode terminal layers 110 'and 210' and the first and second auxiliary
아울러, 상기 제2투명기판(200) 또는 제2투명전극층(210)의 제1투명기판을 향한 면에는 전기변색층(220)이 적층되어 있는데, 상기 전기변색층은 환원반응시 착색(coloration)이 일어나고, 산화반응시 탈색(bleaching) 현상을 발생시키는 재료인 한 특별하게 한정할 것을 아니나, 텅스텐산화물(WOs), 탄탈산화물(TaOs), 나이오븀산화물(NbOs) 또는 몰리브덴산화물(MoOs)을 사용할 수 있으며, 구체적으로 산화텅스텐(WO3), 산화몰리브덴(MoO3), 산화나이오븀(Nb2O5), 산화바나듐(V2O5) 또는 산화티탄(TiO2)으로부터 선택되는 적어도 하나일 수 있으며, 반대로 환원반응시 탈색되고, 산화반응시 착색되는 재료도 채용할 수 있는데, 예를 들면, 수산화이리듐, 수산화니켈, 산화로듐, 산화코발트 등일 수 있다.The
이러한 전기변색층(220)은 다양한 어플레케이션에 적용될 수 있고, 예컨대 창호로 사용하는 경우에 낮에 환원반응에 의하여 착색되어 여름이나 겨울철에 냉난방비의 절감을 도모할 수 있음은 물론, 건물 자체를 창호를 통하여 특정색상이나 이미지로 데커레이션하거나 디스플레이하고자 하는 경우라면 환원반응시에 탈색되는 재료를 사용할 수 있고, 혼합된 형태로도 사용할 수 있다. The
한편, 상기 제1투명기판(100)과 제2투명기판(200)과의 사이에 개재된 전해질(300)은 투명성이 확보되는 브로마이드계화합물(Br composite)로서 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, 4급 암모늄염, 이미다졸륨염 및 피리디늄염으로 이루어지는 군으로부터 선택되는 적어도 하나가 유기용매와 혼합된 액체전해질을 사용할 수 있고 이러한 브로마이드계화합물에는 리튬염을 용해하여 사용할 수 있다.The
또한, 상기 전해질은 리튬염으로서 ClO4, BF4, PF6, OTf(trifluoromethanesulfonate), TFSI(CF3SO2)2N, B(CN)4 작용기와 결합되는 형태로 포함할 수 있으며, 산화환원재료로 Co(III)/Co(II), Fe/Fe+와 같은 금속이온과 같이, 유기용매상 혼합하여 사용할 수 있다. The electrolyte may be in the form of being combined with ClO 4 , BF 4 , PF 6 , trifluoromethanesulfonate (OTf), TFSI (CF 3 SO 2 ) 2 N and B (CN) 4 functional groups as a lithium salt, Such as metal ions such as Co (III) / Co (II) and Fe / Fe + , in an organic solvent.
여기서, 상기 유기용매는 전해질이 산화와 환원반응이 원활하게 수행되는 한 특별히 한정하여 사용할 것은 아니나, 나이트라일계, 락톤계, 설폰계, 카보네이트계, 피롤리돈계 및 아마이드계로 이루어지는 유기용매군으로부터 선택되는 적어도 하나를 용매로 포함할 수 있고, 에틸렌카보네이트, 프로필렌카보네이트, 디메틸카보네이트, 디에틸카보네이트, 에틸메틸카보네이트, 테트라하이드로퓨란 및 감마-부티로락톤으로 이루어진 군으로부터 선택되는 적어도 하나를 각각 또는 혼합하여 사용할 수 있다. Here, the organic solvent is not particularly limited as long as the electrolyte can be efficiently oxidized and reduced. However, the organic solvent may be selected from the group consisting of nitriles, lactones, sulfones, carbonates, pyrrolidones and amides And at least one selected from the group consisting of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, tetrahydrofuran and gamma-butyrolactone, Can be used.
한편, 본 발명의 전해질은 이미다졸리움, 피롤리디움, 피리디니움으로 이루어지는 이온성 액체계 전해질군으로부터 선택되는 적어도 하나를 사용할 수 있으며, 계형 전해질을 사용할 수 있는데, 그 예로는 실리카, 티타니아, 지르코니아와 같은 금속산화물을 평균입도 10 내지 500㎚인 나노입자를 포함할 수 있다.Meanwhile, the electrolyte of the present invention may use at least one selected from the group consisting of imidazolium, pyrrolidium and pyridinium ionic liquid-based electrolytes, and a type electrolyte may be used. Examples thereof include silica, titania, And metal oxide such as zirconia may have nanoparticles having an average particle size of 10 to 500 nm.
실시예Example 1 One
(1) 불소가 도핑된 틴 옥사이드 투명전도성 산화물층(FTO)이 제1투명전극층으로 형성된 투명한 유리기판을 제1투명기판으로 준비하여, 전극단자층과 전극단자층에 연결되도록 50㎛선폭의 보조단자층을 5㎜간격으로 배치하여 패터닝한 스크린으로 실버페이스트를 인쇄하고 경화시키고, 제1투명전극층에 이산화티탄 입자를 포함하는 코팅용조성물을 닥터블레이드법으로 도포하고, 500℃에서 30분 동안 열처리하여, 금속산화물 간의 접촉 및 충진이 이루어지도록 하여 약 8 ㎛ 두께의 금속산화물층을 형성하고, 이를 0.3 mM의 3-methylsalicylic acid가 에탄올에 녹아있는 리간드 용액에 침지하여 24시간 방치후 건조시켜 금속산화물층에 리간드를 흡착시켜 음극계 전극을 제조하였다(경화된 실버전극단자층의 두께 20㎛이었다).(1) A transparent glass substrate in which a fluorine-doped tin oxide transparent conductive oxide layer (FTO) was formed as a first transparent electrode layer was prepared as a first transparent substrate, and an auxiliary A silver paste was printed and cured with a screen patterned with terminal layers arranged at intervals of 5 mm and a coating composition containing titanium dioxide particles was applied to the first transparent electrode layer by a doctor blade method and heat treatment was performed at 500 캜 for 30 minutes A metal oxide layer having a thickness of about 8 占 퐉 was formed by contacting and filling the metal oxide so that 0.3 mM of 3-methylsalicylic acid was immersed in a ligand solution dissolved in ethanol and allowed to stand for 24 hours, (The thickness of the cured silver electrode terminal layer was 20 占 퐉).
(2) 불소가 도핑된 틴 옥사이드 투명전도성 산화물층(FTO)이 제2투명전극층으로 형성된 투명 유리 기판을 제2투명기판으로 준비하고, 상기 제2투명전극층에 텅스텐옥사이드(WO3)을 포함하는 코팅용 조성물을 스크린프린터법으로 도포하고, 450 ℃에서 30분 동안 열처리하여 전기변색층을 형성시키고, 음극계전극과 유사하게 전극단자층과 전극단자층에 연결되도록 50㎛선폭의 보조단자층을 5㎜간격으로 배치하여 패터닝한 스크린으로 실버페이스트를 인쇄하고 경화시켜 양극계 전극을 제조하였다(경화된 실버전극단자층의 두께 20㎛이었다). (2) The fluorine-doped tin oxide transparent conductive oxide layer (FTO) preparing a transparent glass substrate formed of the second transparent electrode layer in the second transparent substrate, and including a tungsten oxide (WO 3) to the second transparent electrode layer The coating composition was coated by a screen printer method and heat treated at 450 캜 for 30 minutes to form an electrochromic layer. An auxiliary terminal layer having a 50 탆 line width was connected to the electrode terminal layer and the electrode terminal layer similarly to the negative electrode A silver paste was printed on a screen patterned at intervals of 5 mm and cured to prepare a positive electrode (the thickness of the cured silver electrode terminal layer was 20 占 퐉).
(3) 상기 제1, 2투명기판을 금속산화물층과 전기변색층이 서로 대향하도록 한 후, 대향된 테두리를 SURLYN(Du Pont사 제조)으로 이루어지는 약 60 ㎛ 두께의 열가소성 고분자층을 개재시켜, 130 ℃의 오븐에 넣어 2분 동안 유지하여 두 전극을 부착하여 밀봉하고, 제1투명기판과 전기변색층을 관통하는 미세 홀을 형성하여 이 홀을 통해 두 전극 사이의 공간에 N,N-dimethylacetamide 용매에 1.0M LiBr을 녹인 전해질 용액을 주입한 다음, 다시 홀의 외부를 접착제로 밀봉하여 본 발명에 따르는 전기변색소자를 제조하였다.(3) After the metal oxide layer and the electrochromic layer were opposed to each other on the first and second transparent substrates, a thermoplastic polymer layer having a thickness of about 60 탆 and made of SURLYN (Du Pont) The substrate was held in an oven at 130 ° C for 2 minutes to attach and seal the two electrodes to form a fine hole passing through the first transparent substrate and the electrochromic layer, and N, N-dimethylacetamide An electrolyte solution in which 1.0 M LiBr was dissolved in a solvent was injected and then the outside of the hole was sealed with an adhesive to prepare an electrochromic device according to the present invention.
실시예2Example 2
리간드 용액 제조 시에, 0.3 mM의 2,3-pyrazine dicarboxylic acid가 녹아있는 리간드용액을 제조하고, 0.5M LiTFSi을 녹인 전해질을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. A ligand solution was prepared in the same manner as in Example 1 except that a ligand solution in which 0.3 mM of 2,3-pyrazine dicarboxylic acid was dissolved was used and an electrolyte in which 0.5 M LiTFSi was dissolved was used.
실시예3Example 3
리간드 용액 제조 시에, 0.3 mM의 Rosmarinic acid가 녹아있는 리간드용액을 제조하고, 0.1M tris(2-(1H-pyrazol-1-yl)pyridine)cobalt(II) bis(trifluoromethylsulphonyl)imide을 녹인 전해질을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. In the preparation of the ligand solution, a ligand solution in which 0.3 mM of Rosmarinic acid was dissolved was prepared and an electrolyte in which 0.1 M tris (2- (1H-pyrazol-1-yl) pyridine) cobalt (II) bis (trifluoromethylsulphonyl) Was used in the same manner as in Example 1,
실시예4Example 4
리간드 용액 제조 시에, 0.3 mM의 Citric acid가 녹아있는 리간드용액을 제조하고, 0.015M tris(2-(1H-pyrazol-1-yl)pyridine)cobalt(III) bis(trifluoromethylsulphonyl)imide를 녹인 전해질을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. In the preparation of the ligand solution, a ligand solution containing 0.3 mM citric acid was prepared and an electrolyte was prepared by dissolving 0.015 M tris (2- (1H-pyrazol-1-yl) pyridine) cobalt (III) bis (trifluoromethylsulphonyl) Was used in the same manner as in Example 1,
실시예5Example 5
리간드 용액 제조 시에, 0.3 mM의 Boric acid가 녹아있는 리간드용액을 제조하고, N-methylpyrrolidone 용매에 1-ethyl-3-methylimidazolium tetracyanoborate을 30wt%로 혼합한 전해질을 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The procedure of Example 1 was repeated except that a ligand solution in which 0.3 mM boric acid was dissolved was prepared and a 1-ethyl-3-methylimidazolium tetracyanoborate was mixed in an amount of 30 wt% in N-methylpyrrolidone solvent. . ≪ / RTI >
실시예6Example 6
리간드 용액 제조 시에, 0.3 mM의 3-methylsalicylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 3-methylsalicylic acid was prepared during the preparation of the ligand solution.
실시예7Example 7
리간드 용액 제조 시에, 0.3 mM의 4-methylsalicylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 4-methylsalicylic acid was prepared at the time of preparing the ligand solution.
실시예8Example 8
리간드 용액 제조 시에, 0.3 mM의 5-methylsalicylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 5-methylsalicylic acid was prepared during the preparation of the ligand solution.
실시예9 Example 9
리간드 용액 제조 시에, 0.3 mM의 4-amino salicylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.A ligand solution was prepared in the same manner as in Example 1, except that a ligand solution in which 0.3 mM of 4-amino salicylic acid was dissolved was prepared.
실시예10 Example 10
리간드 용액 제조 시에, 0.3 mM의 2-hydroxynicotinic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxynicotinic acid was prepared during the preparation of the ligand solution.
실시예11 Example 11
리간드 용액 제조 시에, 0.3 mM의 2-hydroxypicolinic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxypicolinic acid was prepared during the preparation of the ligand solution.
실시예12 Example 12
리간드 용액 제조 시에, 0.3 mM의 2-hydroxy-1-naphthoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxy-1-naphthoic acid was prepared during the preparation of the ligand solution.
실시예13 Example 13
리간드 용액 제조 시에, 0.3 mM의 3-hydroxy-1-naphthoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 3-hydroxy-1-naphthoic acid was prepared during the preparation of the ligand solution.
실시예14 Example 14
리간드 용액 제조 시에, 0.3 mM의 3-hydroxy-2-methyl-4-quinolinecarboxylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 3-hydroxy-2-methyl-4-quinolinecarboxylic acid was prepared during the preparation of the ligand solution.
실시예15 Example 15
리간드 용액 제조 시에, 0.3 mM의 2-hydroxy-3-isopropylbenzoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxy-3-isopropylbenzoic acid was prepared during the preparation of the ligand solution.
실시예16 Example 16
리간드 용액 제조 시에, 0.3 mM의 2-hydroxy-5-(1H-pyrrol-1-yl)benzoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxy-5- (1H-pyrrol-1-yl) benzoic acid was prepared during the preparation of the ligand solution.
실시예17 Example 17
리간드 용액 제조 시에, 0.3 mM의 2-hydroxy-6-methylpyridine-3-carboxylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2-hydroxy-6-methylpyridine-3-carboxylic acid was prepared during the preparation of the ligand solution.
실시예18 Example 18
리간드 용액 제조 시에, 0.3 mM의 2-(4-hydroxyphenylazo)benzoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 2- (4-hydroxyphenylazo) benzoic acid was prepared during the preparation of the ligand solution.
실시예19 Example 19
리간드 용액 제조 시에, 0.3 mM의 1-hydroxy-2-naphthoic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The preparation of the ligand solution was carried out in the same manner as in Example 1, except that 0.3 mM of 1-hydroxy-2-naphthoic acid was dissolved in the ligand solution.
실시예20 Example 20
리간드 용액 제조 시에, 0.3 mM의 4-hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 4-hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid was prepared during the preparation of the ligand solution.
실시예21 Example 21
리간드 용액 제조 시에, 0.3 mM의 3-hydroxy-2-quinoxaline carboxylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 3-hydroxy-2-quinoxaline carboxylic acid was prepared during the preparation of the ligand solution.
실시예22 Example 22
리간드 용액 제조 시에, 0.3 mM의 9-hydroxy-9-fluorene carboxylic acid가 녹아있는 리간드용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다.The procedure of Example 1 was repeated except that a ligand solution containing 0.3 mM of 9-hydroxy-9-fluorene carboxylic acid was prepared during the preparation of the ligand solution.
비교예Comparative Example
리간드 용액 제조를 대신하여, 0.3 mM의 루테늄 디티오시아네이트 2,2′-비피리딜-4,4′-디카르복실레이트를 에탄올에 녹인 염료용액을 제조한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 실시하였다. Except that a dye solution in which 0.3 mM of ruthenium dithiocyanate 2,2'-bipyridyl-4,4'-dicarboxylate was dissolved in ethanol was prepared in place of the preparation of the ligand solution. The same procedure was followed.
시험예Test Example 1 One
상기 실시예 1 내지 22 및 비교예에서 제조한 전기변색소자의 전기적 특성을 평가하기 위하여 염료감응 태양전지의 광전변환 효율을 평가하기 위하여 하기와 같은 방법으로 광전압 및 광전류를 측정하여 광전기적 특성을 관찰하고, 이를 통하여 얻어진 전류밀도(Isc), 전압(Voc), 및 충진계수(fillfactor, ff)를 이용하여 광전변환 효율(ηe)를 하기 수학식 1로 계산하여 표 1에 나타내었다. In order to evaluate the electrical characteristics of the electrochromic devices prepared in Examples 1 to 22 and Comparative Examples, the photoelectric conversion characteristics of the dye-sensitized solar cell were evaluated by measuring the photoelectric voltage and the photocurrent in the following manner The photoelectric conversion efficiency (eta e ) was calculated using the current density I sc , the voltage V oc , and the fill factor ff obtained through the above calculation, and the results are shown in Table 1 below .
이때, 광원으로는 제논 램프(Xenon lamp, Oriel)를 사용하였으며, 상기 제논 램프의 태양조건(AM 1.5)은 표준 태양전지를 사용하여 보정하였다. At this time, a Xenon lamp (Oriel) was used as a light source, and the solar condition (AM 1.5) of the Xenon lamp was corrected using a standard solar cell.
<수학식 1>&Quot; (1) "
ne = (Voc × Isc × ff) / (Pine)n e = (V oc x I sc x ff) / (P ine )
상기 수학식 1에서, (Pine)는 100 ㎽/㎠(1 sun)을 나타낸다. In Equation (1), (P ine ) represents 100 mW / cm 2 (1 sun).
상기와 같이 측정된 값들을 하기 표 1에 나타내었다. The measured values are shown in Table 1 below.
상기 표 1을 참고하면, 본 발명에 따른 실시예를 이용하여 제조된 전기변색소자의 전기적 특성은 비교예에 비하여 낮은 면이 있으나, 오히려 발전회로상 열화를 예방할 수 있어서 장기안정성을 확보할 수 있고, 전기변색소자를 구동하는데 족한 전원을 공급할 수 있음을 알 수 있다. Referring to Table 1, the electrical characteristics of the electrochromic device manufactured using the embodiment of the present invention are lower than those of the comparative example, but rather deterioration in the power generation circuit can be prevented, , It can be seen that a power source suitable for driving the electrochromic device can be supplied.
실험예Experimental Example 2 2
앞서 전압특성을 확인한 실시예 6, 7, 8, 15, 16과 비교예에 대하여, 투과도를 우선적으로 측정하고, 표준 태양전지를 사용하여 보정한 제논 램프의 태양조건(AM 1.5)하에서 전기변색소자를 5분간 노출시켜 전기변색소자의 변색여부, 투과도를 측정하여 실험하여 표 2에 나타내었다. 이때, 전기변색소자의 변색 조건은 단락조건에서 수행하였으며, 착색 후 탈색은 암실에서 단락조건하에서 수행하였다.With respect to Examples 6, 7, 8, 15 and 16 and Comparative Examples in which the voltage characteristics were confirmed in advance, the transmittance was preferentially measured, and under the solar condition (AM 1.5) of the xenon lamp corrected using the standard solar cell, For 5 minutes to measure discoloration and transmittance of the electrochromic device, and the results are shown in Table 2. At this time, the discoloration condition of the electrochromic device was performed under the short-circuit condition, and the discoloration after the coloring was performed under the short-circuit condition in the dark room.
(음극계 전극)*Permeability (%)
(Negative electrode) *
* Tvis : 380nm ~ 780nm 구간에서의 평균 투과율 * Tvis: Average transmittance in a range of 380 nm to 780 nm
** △OD = Log(Tvis(탈색)/Tvis(착색)) ** OD = Log (Tvis (discoloration) / Tvis (discoloration))
또한, 표 2와 도 3, 4, 5를 참고하면, 실시예에 의한 전기변색소자의 투과도가 비교예보다 20 ~ 500% 향상된 것을 확인할 수 있다.Also, referring to Table 2 and FIGS. 3, 4 and 5, it can be seen that the transmittance of the electrochromic device according to the embodiment is improved by 20 to 500% as compared with the comparative example.
즉, 리간드가 흡착된 투명전극층을 포함하는 음극계전극은 리간드의 종류에 상관없이 전파장 영역에서 비슷한 투과도를 가져 투명한 상태를 나타내고 있고, 전기변색층은 전해질로 LiBr를 개재시켜 빛에 조사되면 리간드로부터 여기된 전자가 상대전극으로 이동하여 전기변색층을 환원시킴과 동시에 전해질 내 존재하는 리튬이온이 전기변색층으로 이동하면서 전기변색층이 푸른색으로 변색되는 것을 확인 할 수 있었으며, 이때, 변색되는 정도는 실시예마다 다르게 나타나는데, 5-methylsalicylic acid(실시예 8)> 2-hydroxy-3-isoproylbenzoic acid(실시예 15) > 3-methylsalicylic acid(실시예 6) > 4-methylsalicylic acid(실시예 7) > 2-hydroxy-5-(1H-pyrrol-1-yl)benzoic acid(실시예 16)의 순으로 착색정도가 나타남을 확인할 수 있었다.That is, the negative electrode including the transparent electrode layer having the ligand adsorbed has a transparent state with similar transmittance in the propagation region regardless of the kind of the ligand, and when the electrochromic layer is irradiated with light through LiBr as an electrolyte, The electrons excited by the electrons migrate to the counter electrode to reduce the electrochromic layer, and at the same time, the lithium ions present in the electrolyte migrate to the electrochromic layer, and the electrochromic layer is discolored to blue. Methylsalicylic acid (Example 8)> 2-hydroxy-3-isoproylbenzoic acid (Example 15)> 3-methylsalicylic acid (Example 6)> 4-methylsalicylic acid (Example 7 )> 2-hydroxy-5- (1H-pyrrol-1-yl) benzoic acid (Example 16).
본 발명에 따르는 실시예의 리간드에 포함된 벤젠에서 구조적으로 벤젠링(benzene ring)에 여러 치환기가 도입될 수 있는데, 전기변색 효과를 크게 보이는 것은 hydroxy기의 para위치에 전자주개 작용기(실시예 3)를 도입하는 경우이고, 전자받게 작용기(실시예 5)를 도입하는 경우 상대적으로 전기변색 정도가 작게 나타남을 알 수 있다.In the benzene included in the ligand of the embodiment of the present invention, various substituents can be structurally introduced into the benzene ring. The electrochromic effect of the benzene ring can be enhanced by the fact that the electron donor group (Example 3) And that the degree of electrochromatography is relatively small when the electron acceptor functional group (Example 5) is introduced.
또한, hydroxy기의 meta 위치에 도입하는 작용기의 경우 상대적으로 낮은 전기변색 효과를 보이며, hydroxy기의 ortho위치에 작용기를 도입한 경우 para위치보다는 낮으나 meta위치보다는 우수한 전기변색 효과를 나타냄을 알 수 있다.In addition, the functional group introduced at the meta position of the hydroxy group exhibits a relatively low electrochromic effect, and when the functional group is introduced at the ortho position of the hydroxy group, the electrochromic effect is lower than the para position but superior to the meta position .
한편, 비교예로 사용된 루테늄 염료(N719)의 경우 광전극의 가시광선영역에서의 투과율이 염료에 의해 실시예보다 상당히 낮게 측정되었으며 색 또한 루테늄 염료로 인해 붉은색을 나타내고 있어 시인성이 불리함을 알 수 있다.On the other hand, in the case of the ruthenium dye (N719) used as a comparative example, the transmittance of the photoelectrode in the visible light region was measured to be considerably lower than that in the examples, and the color was also red due to the ruthenium dye, Able to know.
제1투명기판 100, 제1투명전극층 110,
금속산화물층 120, 리간드 130,
제2투명기판 200, 제2투명전극층 210,
전기변색층 220, 전해질 300,
전기변색소자 1000 The first
The second
An
The
Claims (19)
상기 제1투명기판과 대향하여 전해질을 개재시키며 제1투명기판을 향한 면에 전기변색층을 적층한 제2투명기판; 및
제1투명전극층과 전기변색층을 전기적으로 연결시키거나 차단하는 스위칭부;를 포함하고,
상기 제2투명기판과 전기변색층과의 사이에 제2투명전극층을 더 구비하여 일단부에는 제2전극단자층을 구비하고, 타단부에는 제1전극대향부를 구비하며,
상기 제2전극단자층에서 연장되어 전기변색층의 하부에 배치되는 복수개의 제2보조단자층을 구비하고,
상기 제2보조단자층은 실버전극인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
A first transparent substrate having a first transparent electrode layer on which a ligand-adsorbed metal oxide layer is laminated;
A second transparent substrate having an electrochromic layer stacked on a surface facing the first transparent substrate with an electrolyte facing the first transparent substrate; And
And a switching unit electrically connecting or disconnecting the first transparent electrode layer and the electrochromic layer,
A second transparent electrode layer is provided between the second transparent substrate and the electrochromic layer, a second electrode terminal layer is provided at one end, and a first electrode opposing portion is provided at the other end,
And a plurality of second auxiliary terminal layers extending from the second electrode terminal layer and disposed under the electrochromic layer,
Wherein the second auxiliary terminal layer is a silver electrode. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 리간드는 2,3-살리실산(2,3-Salicylic acid), 2,3-피라진디카복실산(2,3-Pyrazine dicarboxylic acid), 로즈마린산(Rosmarinic acid), 시트르산(Citric acid), 붕산(Boric acid), 3-메틸살리실산(3-Methylsalicylic acid), 4-메틸살리실산(4-Methyl salicylic acid), 5-메틸살리실산(5-Methyl salicylic acid), 4-아미노살리실산(4-Aminosalicylic acid), 2-히드록시니코틴산(2-Hydroxynicotinic acid), 3-히드록시피콜리닉산(3-Hydroxypicolinic acid), 2-히드록시-1-나프토산(2-Hydroxy-1-naphthoic acid), 3-히드록시-2-나프토산(3-Hydroxy-2-naphthoic acid), 3-히드록시-2-메틸-4-퀴놀린카복실산(3-Hydroxy-2-methyl-4-quinolinecarboxylic acid), 2-히드록시-3-이소프로필벤조산(2-Hydroxy-3-isopropylbenzoic acid), 2-히드록시-5-(1H-피롤-1-일)벤조산(2-Hydroxy-5-(1H-pyrrol-1-yl)benzoic acid), 2-히드록시-6-메틸피리딘-3-카복실산(2-Hydorxy-6-methylpyridine-3-carboxylic acid), 2-(4-히드록시페닐아조)벤조산(2-(4-Hydroxyphenylazo)benzoic acid), 1-히드록시-2-나프토산(1-Hydroxy-2-naphthoic acid), 4-히드록시-7-트리플루오로메틸-3-퀴놀린카복실산(4-Hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid), 3-히드록시-2-퀴녹살린카복실산(3-Hydroxy-2-quinoxaline carboxylic acid), 9-히드록시-9-플루오렌카복실산(9-Hydroxy-9-fluorene carboxylic acid), 4'-(디페닐아미노)-4-히드록시-[1,1'-비페닐]-3-카복실산(4'-(Diphenylamino)-4-hydroxy-[1,1'-biphenyl]-3-carboxylic acid) 또는 4-(4-(디페닐아미노)스티릴)-2-히드록시벤조산(4-(4-(Diphenylamino)styryl)-2-hydroxybenzoic acid)로부터 선택되는 적어도 하나인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
The ligand may be selected from the group consisting of 2,3-salicylic acid, 2,3-pyrazine dicarboxylic acid, rosmarinic acid, citric acid, boric acid, 4-Methyl salicylic acid, 5-Methyl salicylic acid, 4-Aminosalicylic acid, 2- Hydroxy-1-naphthoic acid, 3-hydroxypicolinic acid, 2-hydroxy-1-naphthoic acid, 3-hydroxy-2-naphthoic acid, 3-hydroxy-2-methyl-4-quinolinecarboxylic acid, 2-hydroxy-3-isopropylbenzoic acid, 2-hydroxy-5- (1H-pyrrol-1-yl) benzoic acid, 2-Hydroxy-6-methylpyridine-3-carboxylic acid, 2- (4-hydroxyphenyl) Hydroxy-2-naphthoic acid, 4-hydroxy-7-trifluoromethyl-3-quinolinecarboxylic acid, 2- 3-quinolinecarboxylic acid, 3-hydroxy-2-quinoxaline carboxylic acid, 9-hydroxy-9-fluorenecarboxylic acid (9- Hydroxy-9-fluorene carboxylic acid, 4 '- (diphenylamino) -4-hydroxy- [1,1'-biphenyl] -3-carboxylic acid (4' - (Diphenylamino) -4- (4- (4- (diphenylamino) styryl) -2-hydroxybenzoic acid) was obtained from 4- (4- Wherein the ligand-metal oxide layer is at least one selected from the group consisting of a metal oxide and a metal oxide.
상기 리간드는 히드록시기가 치환된 벤젠구조를 포함하는 화합물로, 히드록시기의 파라, 메타, 오르토위치에 전자주개작용기가 치환된 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
Wherein the ligand is a compound containing a benzene structure in which a hydroxy group is substituted, wherein the ligand-metal oxide layer is substituted with an electron-former working container at para-, meta- and ortho-positions of the hydroxy group.
상기 전자주개작용기의 위치는 파라, 오르토, 메타순으로 전기변색 정도가 증가되는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method of claim 3,
The electrochromic device according to claim 1, wherein the electrochromic device comprises a ligand-metal oxide layer.
상기 전해질은 브로마이드계화합물을 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
The electrochromic device according to claim 1, wherein the electrolyte comprises a bromide-based compound.
상기 브로마이드계화합물은 브롬화 리튬, 브롬화 나트륨, 브롬화 칼륨, 4급 암모늄염, 이미다졸륨염 및 피리디늄염으로 이루어지는 군으로부터 선택되는 적어도 하나인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
6. The method of claim 5,
Wherein the bromide-based compound is at least one selected from the group consisting of lithium bromide, sodium bromide, potassium bromide, quaternary ammonium salt, imidazolium salt, and pyridinium salt. device.
상기 전해질은 리튬염으로서 ClO4, BF4, PF6, OTf(trifluoromethanesulfonate), TFSI(CF3SO2)2N 또는 B(CN)4 작용기를 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
The electrolyte is a ligand comprising a ClO 4, BF 4, PF 6 , OTf (trifluoromethanesulfonate), TFSI (CF 3 SO 2) 2 N , or B (CN) 4 functional groups as a lithium salt-containing metal oxide layer, The electrochromic device comprising:
상기 리튬염은 산화환원재로 Co(III)/Co(II) 또는 Fe/Fe+을 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
8. The method of claim 7,
Wherein the lithium salt comprises Co (III) / Co (II) or Fe / Fe + as a redox material.
상기 브로마이드계화합물은 리튬염을 더 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
6. The method of claim 5,
Wherein the bromide-based compound further comprises a lithium salt.
상기 전해질은 나이트라일계, 락톤계, 설폰계, 카보네이트계, 피롤리돈계 및 아마이드계로 이루어지는 유기용매군으로부터 선택되는 적어도 하나를 용매로 포함하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
Wherein the electrolyte comprises at least one solvent selected from the group consisting of nitrile, lactone, sulfonate, carbonate, pyrrolidone and amide solvents as a solvent. Electrochromic device.
상기 전해질은 이미다졸리움, 피롤리디움, 피리디니움으로 이루어지는 이온성 액체계 전해질군으로부터 선택되는 적어도 하나인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
Wherein the electrolyte is at least one selected from the group consisting of imidazolium, pyrrolidium, and pyridinium ionic liquid-based electrolytes; and the ligand-metal oxide layer.
상기 전해질은 금속산화물을 평균입균이 10 내지 500㎚인 나노입자를 포함하는 겔형 전해질인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
Wherein the electrolyte is a gel electrolyte including a nanoparticle having a mean particle size of 10-500 nm as a metal oxide, and a ligand-metal oxide layer.
상기 전기변색층은 산화텅스텐(WO3), 산화몰리브덴(MoO3), 산화나이오븀(Nb2O5), 산화바나듐(V2O5), 산화티탄(TiO2), 수산화이리듐, 수산화니켈, 산화로듐 및 산화코발트로 이루어진 군에서 선택된 적어도 하나인 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
Wherein the electrochromic layer comprises at least one of tungsten oxide (WO 3 ), molybdenum oxide (MoO 3 ), niobium oxide (Nb 2 O 5 ), vanadium oxide (V 2 O 5 ), titanium oxide (TiO 2 ) , Rhodium oxide, and cobalt oxide. The magnetic driving electrochromic device according to claim 1, wherein the ligand-metal oxide layer comprises at least one selected from the group consisting of rhodium, rhodium, and cobalt.
상기 제2보조단자층은 10 내지 500㎛의 선폭을 가지는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
And the second auxiliary terminal layer has a line width of 10 to 500 mu m.
상기 제1투명전극층에는 상기 제1전극대향부에 대향되는 부분에 제1전극단자층을 적층하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
The method according to claim 1,
And a first electrode terminal layer is laminated on the first transparent electrode layer at a portion opposed to the first electrode opposing portion.
상기 제1전극단자층에서 연장되어 금속산화물층의 하부에 배치되는 복수개의 제1보조단자층을 구비하는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.
18. The method of claim 17,
And a plurality of first auxiliary terminal layers extending from the first electrode terminal layer and disposed below the metal oxide layer.
상기 제1보조단자층은 10 내지 500 ㎛의 선폭을 가지는 것을 특징으로 하는 리간드-금속산화물층을 포함하는 자기구동 전기변색소자.19. The method of claim 18,
Wherein the first auxiliary terminal layer has a line width of 10 to 500 mu m.
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