CN113741111A - 一种一体式电致变色器件及其制备方法 - Google Patents
一种一体式电致变色器件及其制备方法 Download PDFInfo
- Publication number
- CN113741111A CN113741111A CN202110901358.1A CN202110901358A CN113741111A CN 113741111 A CN113741111 A CN 113741111A CN 202110901358 A CN202110901358 A CN 202110901358A CN 113741111 A CN113741111 A CN 113741111A
- Authority
- CN
- China
- Prior art keywords
- transparent conductive
- electrochromic device
- conductive electrode
- color
- mass ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- -1 polybutylene terephthalate Polymers 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 239000004014 plasticizer Substances 0.000 claims description 11
- 229920005596 polymer binder Polymers 0.000 claims description 11
- 239000002491 polymer binding agent Substances 0.000 claims description 11
- 239000003115 supporting electrolyte Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 5
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- ICIVTHOGIQHZRY-UHFFFAOYSA-N 1-butyl-3-methylimidazol-3-ium;cyanoiminomethylideneazanide Chemical compound [N-]=C=NC#N.CCCCN1C=C[N+](C)=C1 ICIVTHOGIQHZRY-UHFFFAOYSA-N 0.000 claims description 2
- FRZPYEHDSAQGAS-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+]=1C=CN(C)C=1 FRZPYEHDSAQGAS-UHFFFAOYSA-M 0.000 claims description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- JOKVYNJKBRLDAT-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CC[N+]=1C=CN(C)C=1 JOKVYNJKBRLDAT-UHFFFAOYSA-M 0.000 claims description 2
- FRAALLYKYQKVNX-UHFFFAOYSA-N 1-phenyl-4-(1-phenylpyridin-1-ium-4-yl)pyridin-1-ium Chemical compound C1=CC=CC=C1[N+]1=CC=C(C=2C=C[N+](=CC=2)C=2C=CC=CC=2)C=C1 FRAALLYKYQKVNX-UHFFFAOYSA-N 0.000 claims description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229940006460 bromide ion Drugs 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000002834 transmittance Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- YJAHZMNHEWAMNS-UHFFFAOYSA-N CCCCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical compound CCCCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O YJAHZMNHEWAMNS-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JFDZBHWFFUWGJE-KWCOIAHCSA-N benzonitrile Chemical group N#[11C]C1=CC=CC=C1 JFDZBHWFFUWGJE-KWCOIAHCSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K9/02—Organic tenebrescent materials
-
- 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
- G02F1/1516—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 comprising organic material
-
- 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
- G02F1/1516—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 comprising organic material
- G02F1/15165—Polymers
-
- 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
- G02F1/155—Electrodes
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
Abstract
本发明公开了一种一体式电致变色器件及其制备方法，所述一体式电致变色器件的结构分为三层，依次为：透明导电电极一、变色活性层、透明导电电极二；本发明通过选择合适的有机小分子电致变色材料和氧化还原平衡材料，简化了电致变色器件的结构，获得了中性态高透过率、大颜色对比度的一体式电致变色器件，在智能眼镜、智能窗、汽车天窗等领域具有潜在的应用；本发明操作过程简单，原料成本低，安全且无污染，符合绿色生产的要求和保护环境的生态理念。
Description
技术领域
本发明涉及一种透明-深色显示、高光学对比度的一体式电致变色器件及其制备方法，所述电致变色器件在智能眼镜、智能窗、汽车天窗等领域均具有潜在的应用。
背景技术
目前，电致变色器件多为五层的三明治结构，结构依次为透明导电电极一、电致变色层、电解质层、离子储存层、透明导电电极二，结构复杂且制作繁琐。而且大部分电致变色器件为液态型器件和固态型器件。其中，液态型电致变色器件由于其电解质材料是以液态的形式存在，故有易泄漏、安全性低、稳定性差等问题；而固态电致变色器件又有电解质导电率低及其与电极表面接触差等问题。因此，开发新型结构的电致变色器件及其制备工艺尤为重要。
有机小分子电致变色材料(如紫罗精、三苯胺、染料分子等)由于具有分子结构易修饰、颜色可调、光学对比度高，电化学稳定性好等特点得到广泛的研究。但目前大多数基于有机小分子的电致变色器件为液态型，器件组装工艺复杂，且存在漏液等问题。另一方面，目前大多数的有机小分子电致变色器件所采用的氧化还原平衡材料多为二茂铁，因此器件中性态透过率偏低，且存在发黄的效果，限制了其实际应用。
因此，本发明拟以有机小分子作为电致变色材料，选取合适的氧化还原平衡材料，开发一种一体式中性态高透过率、大颜色对比度的电致变色器件及其连续化、大面积的制备方法，有望进一步推动电致变色器件在智能眼镜、智能窗、汽车天窗等领域的应用。
发明内容
针对现有液态电致变色器件结构易泄漏、电化学稳定差，固态电解质的导电率低和电致变色器件结构繁琐等问题，本发明提供了一种一体式电致变色器件及其制备方法。
本发明的技术方案如下：
一种一体式电致变色器件，其结构分为三层，依次为：透明导电电极一、变色活性层、透明导电电极二；
所述透明导电电极一由基底一和透明导电层一构成；
所述透明导电电极二由基底二和透明导电层二构成；
所述基底一或基底二各自独立为玻璃、聚对苯二甲酸丁二酯(PET)、聚氨酯、聚二甲基硅氧烷(PDMS)或透明聚酰亚胺；
所述透明导电层一或透明导电层二各自独立为氧化铟锡、氟掺杂氧化锡或银纳米线；
所述变色活性层与透明导电层一和透明导电层二接触。
本发明所述一体式电致变色器件的制备方法为：
(1)将增塑剂和聚合物粘结剂混合，加热溶胀(75℃，20h)，记为体系A；将支持电解质加入到混合溶剂中，超声溶解，记为体系B；将体系A与体系B混合，超声至均匀，得到混合体系备用；
所述聚合物粘结剂与增塑剂的质量比为1：2～1：5；
所述支持电解质与混合溶剂的质量比为1：2～1：7；
所述体系A与体系B的质量比为1：1～1：5；所述“体系A”、“体系B”没有特殊的含义，标记为“A”、“B”只是用于区分不同的体系；
所述聚合物粘结剂为聚偏氟乙烯、聚氧化乙烯、聚偏氟乙烯-六氟丙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯醇缩丁醛酯或聚乙二醇二甲基丙烯酸酯等；
所述增塑剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯，碳酸二乙酯或N,N-二甲基甲酰胺等；
所述支持电解质为高氯酸锂、四氟硼酸锂、四丁基四氟硼酸铵、四丁基六氟磷酸铵、双三氟甲磺酰亚胺锂、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑二氰胺盐、1-乙基-3-甲基咪唑三氟乙酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑三氟甲磺酸盐或1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐等；
所述混合溶剂为乙腈和二氯甲烷质量比1：2～1：5的混合液；
(2)将氧化还原平衡材料与有机小分子电致变色材料加入到步骤(1)所得混合体系中，超声至均匀，旋蒸除去溶剂，得到凝胶态变色活性层材料；
所述氧化还原平衡材料与有机小分子电致变色材料的质量比为1：2～3：1；
所述有机小分子电致变色材料与混合体系的质量比为1：200～1：300；
所述氧化还原平衡材料为二茂铁、对苯二酚、铁氰化钾、2,2,6,6-四甲基哌啶氧化物、吩噻嗪、吩噁嗪、N,N,N,N-四甲基对苯二胺或三苯胺等；
所述有机小分子电致变色材料的结构如式(I)所示，选自如下物质中的一种或多种：
长烷基链紫精，R和R'上单取代或双取代烷基(例如：乙基、丙基、庚基、辛基或壬基等)；
苯基紫精，R和R'上单取代或双取代苯基或其衍生物(例如：苯乙烯基或苯腈基等)；
磺烷基紫精，R和R'上单取代或双取代磺烷基；
三苯胺基紫精，R和R'上单取代或双取代三苯胺基或其衍生物；
式(I)中，X-为阴离子，可以为溴离子、氯离子或六氟磷酸根离子等；
(3)在透明导电电极二(透明导电层二这侧表面)上黏贴胶框，将步骤(2)所得凝胶态变色活性层材料均匀地涂敷到胶框内，然后将透明导电电极一(透明导电层一这侧表面)盖在胶框上，使透明导电电极一和透明导电电极二贴合并与胶框形成密闭空间，烘干后获得一体式电致变色器件；
所述烘干的温度为40～70℃，时间为12～24h。
与现有技术相比，本发明的有益效果主要体现在：
(1)本发明通过选择合适的有机小分子电致变色材料和氧化还原平衡材料，简化了电致变色器件的结构，获得了中性态高透过率、大颜色对比度的一体式电致变色器件，在智能眼镜、智能窗、汽车天窗等领域具有潜在的应用。
(2)本发明操作过程简单，原料成本低，安全且无污染，符合绿色生产的要求和保护环境的生态理念。
附图说明
图1是一体式电致变色器件的结构示意图；1-透明导电电极一，2-变色活性层，3-透明导电电极二。
图2是实施例1制备的器件变色效果图。
图3是实施例2中制备器件在400～1100nm的全波段透射率图。
图4是实施例3中制备器件在605nm波长处的光学对比度。
图5是实施例3中制备器件在605nm波长处的响应时间测试图。
具体实施方式
下面通过具体实施例进一步描述本发明，但本发明的保护范围并不仅限于此。
以下实施例中使用的导电电极购自辽宁慧特光电，规格：4*2.5，型号：HT-AGC-11。
实施例1：
将2g聚合物粘结剂PVDF和8g增塑剂N,N-二甲基甲酰胺置于30ml试剂瓶中，将该试剂瓶密封后在75℃烘箱中加热溶胀20h，记为体系A；取4g乙腈与10g二氯甲烷的混合液放置在30ml试剂瓶中，然后将3g支持电解质LiBF4加入到混合溶剂中，超声30min至电解质完全溶解，记为体系B；将上述体系A与体系B混合，并将所得混合体系超声30min直至均匀；称取0.1g二壬基紫精和0.15g对苯二酚加入到混合的AB体系，超声至均匀，将所得的溶液通过旋蒸除去溶剂得到凝胶态变色活性层材料。
将带方形孔的3M胶(3M厂家，2.5cm×2.5cm)贴在导电电极二上，将得到的凝胶态变色活性层材料均匀地涂敷到3M胶方框内，最后将导电电极一与3M胶贴紧密贴合。将得到的器件放入到50℃烘箱干燥12h，最终获得一种一体式电致变色器件。
如附图2所示，所制备的一体式电致变色器件在1.3V电压下变成深蓝色；当电压恢复到-0.4V，器件变成透明状态。
实施例2：
与实施例1不同之处在于：聚合物粘结剂、增塑剂、支持电解质、有机小分子电致变色材料和氧化还原平衡材料。具体过程如下：
将2g聚合物粘结剂聚偏氟乙烯-六氟丙烯和10g增塑剂PC置于30ml试剂瓶中，将该试剂瓶密封后在75℃烘箱中加热溶胀20h，记为体系A；取4g乙腈与10g二氯甲烷的混合液放置在30ml试剂瓶中，然后将4g支持电解质四丁基四氟硼酸铵加入到混合溶剂中，超声30min至电解质完全溶解，记为体系B；将上述体系A与体系B混合，并将所得混合体系超声30min直至均匀；称取0.1g二葵基紫精和0.1g吩噁嗪加入混合的AB体系，超声至均匀，将所得的溶液通过旋蒸除去溶剂得到凝胶态变色活性层材料。
将带方形孔的3M胶贴在导电电极二上，将得到的凝胶态变色活性层材料均匀地涂敷到3M胶方框内，最后将导电电极一与3M胶贴紧密贴合。将得到的器件放入到50℃烘箱干燥12h，最终获得一种一体式电致变色器件。
对所述器件进行全波段的透射率测试，采用电化学工作站与紫外光谱仪联用技术，电化学工作站设置为恒电位电解法，紫外光谱设置为全波段透射率，扫描范围为1100～400nm。如附图3所示，器件随着施加电压的不同发生明显变化，平均透射率约75％。
实施例3：
与实施例1不同之处在于：聚合物粘结剂、增塑剂、支持电解质、有机小分子电致变色材料和氧化还原平衡材料。具体过程如下：
将2g聚合物粘结剂PMMA和8g增塑剂PC置于30ml试剂瓶中，将该试剂瓶密封后在75℃烘箱中加热溶胀20h，记为体系A；取4g乙腈与10g二氯甲烷的混合液放置在30ml试剂瓶中，然后将4g支持电解质1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐加入到混合溶剂中，超声30min至电解质完全溶解，记为体系B；将上述体系A与体系B混合，并将所得混合体系超声30min直至均匀；称取0.1g二葵基紫精和0.1g吩噻嗪加入混合的AB体系，超声至均匀，将所得的溶液通过旋蒸除去溶剂得到凝胶态变色活性层材料。
将带方形孔的3M胶贴在导电电极二上，将得到的凝胶态变色活性层材料均匀地涂敷到3M胶方框内，最后将导电电极一与3M胶贴紧密贴合。将得到的器件放入到50℃烘箱干燥12h，最终获得一种一体式电致变色器件。
为了检测所述电致变色器件的响应速度和对比度，我们采用电化学工作站与紫外光谱仪联用技术，电化学工作站设置为多电位阶跃方法：紫外光谱设置为光谱动力学，波长分别设置605nm；初始电位为-0.4V，终止电位为1.3V，电位脉冲宽度为20s，扫描时间为1000s。最终得到的数据如图4和图5所示。器件的在605nm处的光学对比度为72％，响应时间为9.5s(褪色时间)和19s(着色时间)。
Claims (9)
1.一种一体式电致变色器件，其特征在于，所述一体式电致变色器件的结构分为三层，依次为：透明导电电极一、变色活性层、透明导电电极二；
所述透明导电电极一由基底一和透明导电层一构成；
所述透明导电电极二由基底二和透明导电层二构成；
所述基底一或基底二各自独立为玻璃、聚对苯二甲酸丁二酯、聚氨酯、聚二甲基硅氧烷或透明聚酰亚胺；
所述透明导电层一或透明导电层二各自独立为氧化铟锡、氟掺杂氧化锡或银纳米线；
所述变色活性层与透明导电层一和透明导电层二接触。
2.如权利要求1所述一体式电致变色器件的制备方法，其特征在于，所述的制备方法为：
(1)将增塑剂和聚合物粘结剂混合，加热溶胀，记为体系A；将支持电解质加入到混合溶剂中，超声溶解，记为体系B；将体系A与体系B混合，超声至均匀，得到混合体系备用；
所述聚合物粘结剂为聚偏氟乙烯、聚氧化乙烯、聚偏氟乙烯-六氟丙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇、聚乙烯醇缩丁醛酯或聚乙二醇二甲基丙烯酸酯；
所述增塑剂为碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯，碳酸二乙酯或N,N-二甲基甲酰胺；
所述支持电解质为高氯酸锂、四氟硼酸锂、四丁基四氟硼酸铵、四丁基六氟磷酸铵、双三氟甲磺酰亚胺锂、1-丁基-3-甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑二氰胺盐、1-乙基-3-甲基咪唑三氟乙酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑三氟甲磺酸盐或1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐；
所述混合溶剂为乙腈和二氯甲烷质量比1：2～1：5的混合液；
(2)将氧化还原平衡材料与有机小分子电致变色材料加入到步骤(1)所得混合体系中，超声至均匀，旋蒸除去溶剂，得到凝胶态变色活性层材料；
所述氧化还原平衡材料为二茂铁、对苯二酚、铁氰化钾、2,2,6,6-四甲基哌啶氧化物、吩噻嗪、吩噁嗪、N,N,N,N-四甲基对苯二胺或三苯胺；
所述有机小分子电致变色材料的结构如式(I)所示，选自如下物质中的一种或多种：
长烷基链紫精，R和R'上单取代或双取代烷基；
苯基紫精，R和R'上单取代或双取代苯基或其衍生物；
磺烷基紫精，R和R'上单取代或双取代磺烷基；
三苯胺基紫精，R和R'上单取代或双取代三苯胺基或其衍生物；
式(I)中，X-为溴离子、氯离子或六氟磷酸根离子；
(3)在透明导电电极二上黏贴胶框，将步骤(2)所得凝胶态变色活性层材料均匀地涂敷到胶框内，然后将透明导电电极一盖在胶框上，使透明导电电极一和透明导电电极二贴合并与胶框形成密闭空间，烘干后获得一体式电致变色器件。
3.如权利要求2所述的制备方法，其特征在于，步骤(1)中，所述加热溶胀的温度为75℃，时间为20h。
4.如权利要求2所述的制备方法，其特征在于，步骤(1)中，所述聚合物粘结剂与增塑剂的质量比为1：2～1：5。
5.如权利要求2所述的制备方法，其特征在于，步骤(1)中，所述支持电解质与混合溶剂的质量比为1：2～1：7。
6.如权利要求2所述的制备方法，其特征在于，步骤(1)中，所述体系A与体系B的质量比为1：1～1：5。
7.如权利要求2所述的制备方法，其特征在于，步骤(2)中，所述氧化还原平衡材料与有机小分子电致变色材料的质量比为1：2～3：1。
8.如权利要求2所述的制备方法，其特征在于，步骤(2)中，所述有机小分子电致变色材料与混合体系的质量比为1：200～1：300。
9.如权利要求2所述的制备方法，其特征在于，步骤(3)中，所述烘干的温度为40～70℃，时间为12～24h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110901358.1A CN113741111B (zh) | 2021-08-06 | 2021-08-06 | 一种一体式电致变色器件及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110901358.1A CN113741111B (zh) | 2021-08-06 | 2021-08-06 | 一种一体式电致变色器件及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113741111A true CN113741111A (zh) | 2021-12-03 |
| CN113741111B CN113741111B (zh) | 2023-11-10 |
Family
ID=78730352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110901358.1A Active CN113741111B (zh) | 2021-08-06 | 2021-08-06 | 一种一体式电致变色器件及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113741111B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957275A (zh) * | 2022-06-08 | 2022-08-30 | 吉林大学 | 有机小分子电致变色材料、膜、器件及其制备方法 |
| CN114967264A (zh) * | 2022-06-10 | 2022-08-30 | 苏州新吴光电股份有限公司 | 一种电致变色凝胶和防眩光智能玻璃 |
| CN115057867A (zh) * | 2022-06-08 | 2022-09-16 | 吉林大学 | 一种电致变色化合物、器件及其制备方法和应用 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673018A (zh) * | 2008-09-10 | 2010-03-17 | 财团法人工业技术研究院 | 太阳光电电致变色器件 |
| CN104130769A (zh) * | 2014-08-01 | 2014-11-05 | 北京大学 | 一种电致变色功能材料及电致变色器件 |
| CN105372896A (zh) * | 2015-11-20 | 2016-03-02 | 浙江工业大学 | 基于导电聚合物的固体电解质电致变色柔性器件的制备 |
| CN105954954A (zh) * | 2016-06-23 | 2016-09-21 | 上海师范大学 | 一种固态电致变色器件及其制备方法与应用 |
| CN106479478A (zh) * | 2015-08-24 | 2017-03-08 | 北京大学 | 一种基于金属纳米粒子的电致变色材料及器件 |
| CN107779190A (zh) * | 2016-08-24 | 2018-03-09 | 芝普企业股份有限公司 | 电致变色材料及具有该电致变色材料的防眩后视镜 |
| CN110632803A (zh) * | 2019-09-20 | 2019-12-31 | 长春工业大学 | 一种柔性电致变色器件及其制备方法 |
-
2021
- 2021-08-06 CN CN202110901358.1A patent/CN113741111B/zh active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101673018A (zh) * | 2008-09-10 | 2010-03-17 | 财团法人工业技术研究院 | 太阳光电电致变色器件 |
| CN104130769A (zh) * | 2014-08-01 | 2014-11-05 | 北京大学 | 一种电致变色功能材料及电致变色器件 |
| CN106479478A (zh) * | 2015-08-24 | 2017-03-08 | 北京大学 | 一种基于金属纳米粒子的电致变色材料及器件 |
| CN105372896A (zh) * | 2015-11-20 | 2016-03-02 | 浙江工业大学 | 基于导电聚合物的固体电解质电致变色柔性器件的制备 |
| CN105954954A (zh) * | 2016-06-23 | 2016-09-21 | 上海师范大学 | 一种固态电致变色器件及其制备方法与应用 |
| CN107779190A (zh) * | 2016-08-24 | 2018-03-09 | 芝普企业股份有限公司 | 电致变色材料及具有该电致变色材料的防眩后视镜 |
| CN110632803A (zh) * | 2019-09-20 | 2019-12-31 | 长春工业大学 | 一种柔性电致变色器件及其制备方法 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957275A (zh) * | 2022-06-08 | 2022-08-30 | 吉林大学 | 有机小分子电致变色材料、膜、器件及其制备方法 |
| CN115057867A (zh) * | 2022-06-08 | 2022-09-16 | 吉林大学 | 一种电致变色化合物、器件及其制备方法和应用 |
| CN115057867B (zh) * | 2022-06-08 | 2023-09-15 | 吉林大学 | 一种电致变色化合物、器件及其制备方法和应用 |
| CN114957275B (zh) * | 2022-06-08 | 2023-09-29 | 吉林大学 | 有机小分子电致变色材料、膜、器件及其制备方法 |
| CN114967264A (zh) * | 2022-06-10 | 2022-08-30 | 苏州新吴光电股份有限公司 | 一种电致变色凝胶和防眩光智能玻璃 |
| CN114967264B (zh) * | 2022-06-10 | 2024-01-12 | 苏州新吴光电股份有限公司 | 一种电致变色凝胶和防眩光智能玻璃 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113741111B (zh) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113741111B (zh) | 一种一体式电致变色器件及其制备方法 | |
| Alesanco et al. | Multicolor electrochromics: rainbow-like devices | |
| JP6812135B2 (ja) | エレクトロクロミック素子 | |
| US20090242113A1 (en) | Gel polymer electrolytes | |
| Oh et al. | User-customized, multicolor, transparent electrochemical displays based on oxidatively tuned electrochromic ion gels | |
| US20060203322A1 (en) | Gel polymers containing ionic liquids | |
| CN104698717A (zh) | 凝胶状的聚合物电解质以及基于导电聚合物的固态电致变色器件的制备方法 | |
| CN103477407A (zh) | 电极复合体和配备有它的光电元件 | |
| CN105372896A (zh) | 基于导电聚合物的固体电解质电致变色柔性器件的制备 | |
| CN108873537B (zh) | 一种电致变色薄膜、其制备方法和应用以及电致变色器件 | |
| Zhang et al. | Visible and infrared electrochromism of bis (2-(2-(2-hydroxyethoxy) ethoxy) ethyl) viologen with sodium carboxymethyl chitosan-based hydrogel electrolytes | |
| CN110716360B (zh) | 一种高性能全固态聚合物电致变色器件及其制备方法 | |
| CN113025304A (zh) | 一种电致变色材料及其制备方法和应用 | |
| CN110928095A (zh) | 一种能够实现在任意颜色之间转变的双电致变色层器件及组装方法 | |
| Feng et al. | An overview of electrochromic devices with electrolytes containing viologens | |
| Puguan et al. | Engineered ionene/pnipam hybrid dual-response material generating tunable and unique optical modes for adaptive solar transmittance modulation | |
| US10104744B2 (en) | Infrared modulating electro-fluorescence device | |
| Pan et al. | All-in-one electrochromic devices with biological tissues used as electronic components | |
| Pan et al. | Electrochromic materials containing pyridinium salt and benzoate moieties with dual-colored and long-life performance | |
| KR102038495B1 (ko) | 전기 변색 화합물, 전기 변색 소자, 및 이의 구동 방법 | |
| Meng | Organic Electronics for Electrochromic Materials and Devices | |
| Ah et al. | Optical and electrical properties of electrochromic devices depending on electrolyte concentrations and cell gaps | |
| Sun et al. | Viologens and extended viologen derivatives with mono-and di-hexyl substituents for highly stable all-in-one ECDs and solar cell powered large-area ECDs | |
| CN112666770B (zh) | 基于p(spma-mma)水凝胶电解质的电致变色柔性器件及其制备方法及应用 | |
| KR102052440B1 (ko) | 전기 변색성 슈퍼 커패시터 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |