CN117799197A - Large-area electrochromic device and preparation method thereof - Google Patents
Large-area electrochromic device and preparation method thereof Download PDFInfo
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- CN117799197A CN117799197A CN202311804770.7A CN202311804770A CN117799197A CN 117799197 A CN117799197 A CN 117799197A CN 202311804770 A CN202311804770 A CN 202311804770A CN 117799197 A CN117799197 A CN 117799197A
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- electrochromic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 polyethylene Polymers 0.000 claims description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 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
- 238000004519 manufacturing process Methods 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002042 Silver nanowire Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 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 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims description 3
- TTWSHOZCUVAKIN-UHFFFAOYSA-N 2,4-dimethoxythiophene Chemical compound COC1=CSC(OC)=C1 TTWSHOZCUVAKIN-UHFFFAOYSA-N 0.000 claims description 3
- CGWGNMXPEVGWGB-UHFFFAOYSA-N 2-hydroxy-1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=C(CCO)C=C1 CGWGNMXPEVGWGB-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- KHDZXBKJADQNKK-UHFFFAOYSA-N P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KHDZXBKJADQNKK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 229940006460 bromide ion Drugs 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- KOMLXUNAWWFLRU-UHFFFAOYSA-N lithium;trifluoromethanesulfonamide Chemical compound [Li].NS(=O)(=O)C(F)(F)F.NS(=O)(=O)C(F)(F)F KOMLXUNAWWFLRU-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 2
- 238000005562 fading Methods 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 61
- 239000007787 solid Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000526 short-path distillation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
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
- G02F1/1506—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 caused by electrodeposition, e.g. electrolytic deposition of an inorganic material on or close to an electrode
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a large-area electrochromic device and a preparation method thereof, wherein the structure of the large-area electrochromic device is divided into 5 layers, namely a first transparent supporting layer, a first transparent conductive electrode layer, an electrochromic layer, a second transparent conductive electrode layer and a second transparent supporting layer in sequence; the invention simplifies the structure of the electrochromic device by selecting proper organic micromolecular electrochromic material, redox balance material, proper film forming equipment and process, and obtains the large-area electrochromic device with high transmittance in the fading state, pure black in the coloring state and high color contrast.
Description
Technical Field
The invention relates to the technical field of electrochromic devices, in particular to a large-area electrochromic device and a preparation method thereof.
Background
Currently, most electrochromic devices are of a seven-layer sandwich structure, and the structure sequentially comprises a first transparent supporting layer, a first transparent conductive electrode layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a second transparent conductive electrode layer and a second transparent supporting layer; the structure is complex, the process steps are more, and the yield is low, so that the development of the electrochromic device with simple structure and few process steps and the preparation process are particularly important.
Organic small molecule electrochromic materials (such as viologen, triphenylamine, dye molecules and the like) are widely studied due to the characteristics of simple molecular structure, environment-friendly synthesis process, adjustable color, high optical contrast, good electrochemical stability and the like, but devices based on the small molecule electrochromic materials are mostly liquid electrolytes, and the manufactured devices are easy to have the risk of liquid leakage, so that the practical use of the devices is limited.
Therefore, the invention aims to modify and screen proper electrochromic materials and electrolyte materials, develop an electrochromic device with high electrochemical contrast of a single layer, simple processing technology and high cycle stability, and is expected to further push the electrochromic device to be applied to the fields of intelligent windows, automobile skylights and the like.
Disclosure of Invention
Aiming at the problems of easy liquid leakage, complex structure, multiple processing process flows and low yield of liquid electrolyte, the invention provides a single-layer large-area electrochromic device and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a large-area electrochromic device, comprising the steps of:
(a) Mixing a polymer and a polymer dispersing agent, heating, stirring and dissolving to obtain a system A; adding electrolyte into the mixed solvent, and performing ultrasonic dissolution to obtain a system B; mixing the system A with the system B, adding a supporting material, ultrasonically mixing until the mixture is clear, and filtering to obtain a mixed system C;
the polymer is one or more of polyethylene, polyvinylidene fluoride, polyethylene oxide, polypropylene, polyacrylonitrile, polyacrylate, polymethyl methacrylate, polyvinyl alcohol, polyvinyl carbonate, polypropylene carbonate, polymethyl carbonate, polyethylene carbonate and polyurethane; the polymer dispersing agent is one or more of water, acetonitrile, methanol, ethanol, methylene dichloride, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene, paraxylene and ethyl acetate; the mass ratio of the polymer to the polymer dispersing agent is 1:2-1:10;
the electrolyte is one or more of lithium perchlorate, lithium tetrafluoroborate, ammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, lithium chloride, bis (trifluoromethanesulfonamide) lithium, 1-ethyl-3-methylimidazole trifluorophosphate, 1-butyl-3-methylimidazole trifluorophosphate, 1-ethyl-3-methylimidazole trifluorosulfonate, ferrocene, hydroquinone, potassium ferricyanide, 2, 6-tetramethylpiperidine, 2, 4-dimethoxy thiophene, tetramethyl p-phenylenediamine, p-phenylenediamine and p-methylaniline; the mixed solvent is at least two of deionized water, acetonitrile, methanol, ethanol, dichloromethane, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene and p-toluene; the dosage ratio of the electrolyte to the mixed solvent is (0.4-7) g: (20-160) mL; the mass ratio of the polymer to the electrolyte is 4-5: 1, a step of;
the supporting material is one or more of propylene acetate, propylene carbonate, ethylene carbonate, dimethyl carbonate and diethyl carbonate; the mass ratio of the polymer to the supporting material is 10:1-1:1;
(b) Adding the electrochromic material into the mixed system C, and performing ultrasonic or stirring dispersion until the electrochromic material is uniform to obtain a mixed system D; the mass ratio of the polymer to the electrochromic material in the step (a) is 50-150:1;
the electrochromic material is selected from one or more of materials shown in formulas (I), (II) and (III);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Is one or two of hydrogen, methyl, ethyl, acetyl, methoxy, acetamido, phenethyl, p-methylphenylethyl, 2, 4-dimethylphenylethyl, p-ethylphenyl ethyl and p-acetamido phenethyl, wherein X - Is chloride ion, bromide ion or hexafluorophosphate ion;
(c) Adding the photoinitiator into the mixed system D, carrying out light-shielding ultrasonic treatment or stirring and dispersing until the mixture is uniform, removing most of the mixed solvent by rotary evaporation, and distilling to remove all the solvent to obtain electrochromic layer gel;
the photoinitiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-hydroxy-4' - (2-hydroxyethyl) -2-methyl propiophenone, phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite and iodonium salt, and the mass ratio of electrochromic material to photoinitiator is (10-100) 1;
(d) And respectively conveying the two composite films into a pair of rotating rollers (7) of a roll-to-roll compounding machine, dripping the electrochromic layer gel between the two composite films through a feed pipe (6), compounding the two composite films through a roll-to-roll process, preparing a wet film with uniform thickness, and forming a dry film after the wet film is irradiated and solidified by an ultraviolet lamp (8), namely the electrochromic device.
In step (a), the polymer is dissolved with stirring at 60-80 ℃.
In the step (c), the spin-steaming temperature is 60-100 ℃, the pressure is-0.05 to-0.2 MPaG, the time is 1-5 h, and 70-98wt% of solvent is distilled out.
In the step (c), the distillation temperature is 70-130 ℃, the pressure is-0.1-0.8 MPaG, the time is 0.1-1 h, and the solvent content after evaporation is less than 0.05wt%.
In the step (d), the feeding pipe (6) can axially move back and forth along the double-roller gap; the rotation speeds of the two rollers are the same, the rotation directions are opposite, and the rotation speed is 10-100 rpm; the gap between the two rollers is adjustable, and the adjustable range is 10 um-300 um.
In the step (d), the irradiation wavelength of the ultraviolet lamp (8) is 200 nm-400 nm, and the power density is 10-120 w/cm.
In the step (d), the thickness of the wet film is 20-200 um, and the thickness of the dry film is 15-200 um.
In the step (d), the composite film is formed by compounding a film made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene and transparent polyimide with an indium tin oxide electrode layer or a fluorine-doped tin oxide electrode layer or a silver nanowire electrode layer.
The large-area electrochromic device comprises a first transparent supporting layer, a first transparent conductive electrode layer, an electrochromic layer, a second transparent conductive electrode layer and a second transparent supporting layer which are stacked from top to bottom, wherein the first transparent supporting layer and the second transparent supporting layer are films made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene and transparent polyimide; the first transparent conductive electrode layer and the second transparent conductive electrode layer are indium tin oxide electrode layers or fluorine-doped tin oxide electrode layers or silver nanowire electrode layers.
The beneficial effects of the invention are as follows: the invention improves the structure of the electrochromic layer by improving the electrochromic material, integrates the conventional electrochromic layer, the electrolyte layer and the ion storage layer into a novel electrochromic layer, adopts a roll-to-roll processing method, forms at one time, has few manufacturing steps and high yield, and the prepared electrochromic device has high electrochemical contrast and high cycling stability, and can be applied to the fields of intelligent windows, automobile skylights and the like.
Drawings
FIG. 1 is a schematic diagram of the structure of a large area electrochromic device;
FIG. 2 is a schematic diagram of a large area electrochromic device fabrication;
FIG. 3 is a photochemistry contrast ratio plot of the electrochromic device prepared in example 1;
FIG. 4 is a graph of the stability of the electrochromic device prepared in example 1;
in the figure: the transparent electrode comprises a first transparent supporting layer 1, a first transparent conductive electrode layer 2, an electrochromic layer 3, a second transparent conductive electrode layer 4, a second transparent supporting layer 5, a feeding pipe 6, a rotary roller 7 and an ultraviolet lamp 8.
Detailed Description
The invention is further described with reference to the drawings and detailed description which follow:
the invention simplifies the structure of the electrochromic device by selecting proper organic micromolecular electrochromic material, redox balance material (polymer, electrolyte and supporting material) and proper film forming equipment and process, and obtains the large-area electrochromic device with high transmittance in the fading state, pure black in the coloring state and high color contrast, which comprises the following steps:
(a) Mixing a polymer and a polymer dispersing agent, heating to 60-80 ℃ and stirring for dissolution to obtain a system A; adding electrolyte into the mixed solvent, and performing ultrasonic dissolution to obtain a system B; mixing the system A with the system B, adding a supporting material, ultrasonically mixing until the mixture is clear, and filtering to obtain a mixed system C.
Wherein the polymer is one or more of polyethylene, polyvinylidene fluoride, polyethylene oxide, polypropylene, polyacrylonitrile, polyacrylate, polymethyl methacrylate, polyvinyl alcohol, polyvinyl carbonate, polypropylene carbonate, polymethyl carbonate, polyethylene carbonate and polyurethane; the polymer dispersing agent is one or more of water, acetonitrile, methanol, ethanol, methylene dichloride, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene, paraxylene and ethyl acetate; the mass ratio of the polymer to the polymer dispersing agent is 1:2-1:10;
the electrolyte is one or more of lithium perchlorate, lithium tetrafluoroborate, ammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, lithium chloride, bis (trifluoromethanesulfonamide) lithium, 1-ethyl-3-methylimidazole trifluorophosphate, 1-butyl-3-methylimidazole trifluorophosphate, 1-ethyl-3-methylimidazole trifluorosulfonate, ferrocene, hydroquinone, potassium ferricyanide, 2, 6-tetramethylpiperidine, 2, 4-dimethoxy thiophene, tetramethyl p-phenylenediamine, p-phenylenediamine and p-methylaniline; the mixed solvent is at least two of deionized water, acetonitrile, methanol, ethanol, dichloromethane, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene and p-toluene; the dosage ratio of the electrolyte to the mixed solvent is (0.4-7) g: (20-160) mL; the mass ratio of the polymer to the electrolyte is 4-5: 1, a step of;
the supporting material is one or more of propylene acetate, propylene carbonate, ethylene carbonate, dimethyl carbonate and diethyl carbonate; the mass ratio of the polymer to the supporting material is 10:1-1:1;
(b) Adding the electrochromic material into the mixed system C, and performing ultrasonic or stirring dispersion until the electrochromic material is uniform to obtain a mixed system D; the mass ratio of the polymer to the electrochromic material in the step (a) is 50-150:1;
the electrochromic material is selected from one or more of materials shown in formulas (I), (II) and (III);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Is one or two of hydrogen, methyl, ethyl, acetyl, methoxy, acetamido, phenethyl, p-methylphenylethyl, 2, 4-dimethylphenylethyl, p-ethylphenyl ethyl and p-acetamido phenethyl, wherein X - Is chloride ion, bromide ion or hexafluorophosphate ion;
(c) Adding the photoinitiator into the mixed system D, carrying out light-shielding ultrasonic treatment or stirring and dispersing until the mixture is uniform, carrying out rotary evaporation under the conditions of 60-100 ℃ and-0.05 to-0.2 MPaG, evaporating 70-98 wt% of solvent, carrying out distillation under the conditions of 70-130 ℃ and-0.1 to-0.8 MPaG for 0.1-1 h, and removing the solvent (the content of the solvent after evaporation is less than 0.05 wt%) to obtain the electrochromic layer gel.
The photoinitiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-hydroxy-4' - (2-hydroxyethyl) -2-methyl propiophenone, phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite and iodonium salt, and the mass ratio of electrochromic material to photoinitiator is (10-100) 1;
(d) The two composite films are respectively conveyed into a pair of rotating rollers 7 of a roll-to-roll compounding machine, electrochromic layer gel is dripped between the two composite films through a feeding pipe 6, the two composite films are compounded through a roll-to-roll process, a wet film (with the thickness of 20-200 um) with uniform thickness is prepared, and after the wet film is irradiated and solidified through an ultraviolet lamp 8 (the irradiation wavelength is 200-400 nm and the power density is 10-120 w/cm), a dry film with the thickness of 15-200 um is formed, namely the electrochromic device. Wherein the feeding pipe 6 can axially move back and forth along the double-roller gap; the rotation speeds of the two rollers are the same, the rotation directions are opposite, and the rotation speed is 10-100 rpm; the gap between the two rollers is adjustable, and the adjustable range is 10 um-300 um. A schematic of a large area electrochromic device fabricated by a roll-to-roll process is shown in fig. 2.
The composite film is formed by compounding a film made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene and transparent polyimide with an indium tin oxide electrode layer or a fluorine-doped tin oxide electrode layer or a silver nanowire electrode layer. The composite membrane was purchased from Dongguan city, jierou New Material Co.
The large-area electrochromic device prepared by the method comprises a first transparent supporting layer 1, a first transparent conductive electrode layer 2, an electrochromic layer 3, a second transparent conductive electrode layer 4 and a second transparent supporting layer 5 which are stacked from top to bottom, wherein the first transparent supporting layer 1 and the second transparent supporting layer 5 are films made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene and transparent polyimide; the first transparent conductive electrode layer 2 and the second transparent conductive electrode layer 4 are indium tin oxide electrode layers or fluorine-doped tin oxide electrode layers or silver nanowire electrode layers.
Preferred embodiments are as follows:
example 1
Placing 2g of polyacrylate and 5g of ethyl acetate into a 30mL container, heating to 80 ℃ and stirring to dissolve for 24h until the solid is completely dissolved, and recording a system A; putting 0.2g of lithium perchlorate and 0.3g of lithium tetrafluoroborate into a 30mL container, adding 10mL of deionized water and 10mL of methanol, and performing ultrasonic treatment for 3 hours until the solid is completely dissolved, and recording a system B; pouring the system A and the system B into a 100mL container, adding 0.5g of propylene carbonate, uniformly dispersing by ultrasonic waves, and filtering to obtain a system C; adding 0.2g of acetamido disubstituted viologen into the system C, uniformly dispersing by ultrasonic waves, and marking as a system D; adding 0.02g of TPO into the system D, stirring and dispersing for 2 hours at 90 ℃ in a dark place, removing most of the solvent by rotary evaporation of-0.1 MPaG, and removing the solvent by short-path distillation of-0.5 MPaG at 100 ℃ to obtain an electrochromic gel material for standby; the distance between the two rollers is adjusted to 120um, the rotating speed is 20rmp, the speed of the feeding pipe 6 is 5mL/min, the moving speed is 20cm/min, the two rollers are started after the feeding pipe 6 is opened for 10s, an ultraviolet light source (the irradiation wavelength is 200nm, the power density is 100 w/cm) is opened, the two composite films are respectively transmitted into a pair of rotating rollers 7 of a roll-to-roll compounding machine, electrochromic layer gel is dripped between the two composite films through the feeding pipe 6, the two composite films are compounded through a roll-to-roll process, a wet film is prepared, the wet film is irradiated and solidified through an ultraviolet lamp 8, a dry film is formed, the device is taken down after film formation is completed, and the unfilled part of the electrochromic layer is cut off, so that the large-area electrochromic device is prepared.
Example 2
Placing 2g of polyvinyl carbonate and 6g of toluene in a 30mL container, heating to 60 ℃ and stirring for dissolving for 24h until the solid is completely dissolved, and recording a system A; putting 0.2g of lithium perchlorate and 0.3g of ferrocene into a 30mL container, adding 10mL of deionized water and 10mL of methanol, and performing ultrasonic treatment for 3 hours until the solid is completely dissolved, and recording a system B; pouring the system A and the system B into a 100mL container, adding 0.5g of propylene carbonate, uniformly dispersing by ultrasonic waves, and filtering to obtain a system C; adding 0.3g of p-methyl phenethyl disubstituted viologen and 0.1g of diacetyl amino substituted thiophene into the system C, and uniformly dispersing by ultrasonic waves, wherein the system D is marked; adding 0.03g of TPO into the system D, stirring and dispersing for 2 hours at 90 ℃ in a dark place, removing most of the solvent by rotary evaporation of-0.1 MPaG, and removing the solvent by short-path distillation of-0.4 MPaG at 100 ℃ to obtain an electrochromic gel material for standby; the distance between the two rollers is adjusted to 120um, the rotating speed is 30rmp, the speed of the feeding pipe 6 is 8mL/min, the moving speed is 25cm/min, the two rollers are started after the feeding pipe 6 is opened for 8s, an ultraviolet light source (the irradiation wavelength is 200nm, the power density is 90 w/cm) is opened, the two composite films are respectively transmitted into a pair of rotating rollers 7 of a roll-to-roll compounding machine, electrochromic layer gel is dripped between the two composite films through the feeding pipe 6, the two composite films are compounded through a roll-to-roll process, a wet film is prepared, the wet film is irradiated and solidified through an ultraviolet lamp 8, a dry film is formed, the device is taken down after film formation is completed, and the unfilled part of the electrochromic layer is cut off, so that the large-area electrochromic device is prepared.
Example 3
Placing 2g of polypropylene carbonate and 5g of toluene in a 30mL container, heating to 90 ℃ and stirring for dissolving for 24h until the solid is completely dissolved, and recording a system A; putting 0.2g of tetrabutylammonium tetrafluoroborate, 0.1g of hydroquinone and 0.1g of potassium ferricyanide into a 30mL container, adding 10mL of deionized water, 10mL of methanol, and carrying out ultrasonic treatment for 3 hours until the solid is completely dissolved, and recording a system B; pouring the system A and the system B into a 100mL container, adding 0.5g of diethyl carbonate, uniformly dispersing by ultrasonic waves, filtering and marking as a system C; adding 0.3g of 2, 4-dimethylbenzene ethyl disubstituted viologen and 0.2g of phenethyl disubstituted thiophene into the system C, and uniformly dispersing by ultrasonic waves, wherein the system D is marked; adding 0.04g (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide into the system D, stirring and dispersing for 4 hours at 90 ℃ in a dark place, removing most of the solvent by rotary evaporation of-0.1 MPaG, and removing the solvent by short-path distillation of-0.5 MPaG at 120 ℃ to obtain an electrochromic gel material for standby; the distance between the two rollers is adjusted to 110um, the rotating speed is 30rmp, the speed of the feeding pipe 6 is 8mL/min, the moving speed is 30cm/min, the two rollers are started after the feeding pipe 6 is opened for 8s, an ultraviolet light source is opened (the irradiation wavelength is 200nm, the power density is 120 w/cm), the two composite films are respectively transmitted into a pair of rotating rollers 7 of a roll-to-roll compounding machine, electrochromic layer gel is dripped between the two composite films through the feeding pipe 6, the two composite films are compounded through a roll-to-roll process, a wet film is prepared, the wet film is irradiated and solidified through an ultraviolet lamp 8, a dry film is formed, the device is taken down after film formation is completed, and the unfilled part of the electrochromic layer is cut off, so that the large-area electrochromic device is prepared.
Example 4
Placing 30g of polyurethane and 200g of N, N-dimethylformamide into a 500mL container, heating to 80 ℃ and stirring to dissolve for 24 hours until the solid is completely dissolved, and recording a system A; putting 2g of lithium perchlorate and 5g of lithium tetrafluoroborate into a 250mL container, adding 80mL of deionized water and 80mL of methanol, and performing ultrasonic treatment for 3 hours until the solid is completely dissolved, and recording a system B; pouring the system A and the system B into a 1000mL container, adding 25g of propylene carbonate, uniformly dispersing by ultrasonic waves, filtering and marking as a system C; adding 12g of acetaminophen ethyl disubstituted viologen and 7g of 2, 4-dimethylbenzene ethyl disubstituted thiophene into the system C, and uniformly dispersing by ultrasonic waves, wherein the system D is marked; adding 0.2g of TPO into the system D, stirring and dispersing for 2 hours at 90 ℃ in a dark place, removing most of the solvent by rotary evaporation of-0.1 MPaG, and removing the solvent by short-path distillation of-0.5 MPaG at 100 ℃ to obtain an electrochromic gel material for standby; the distance between the two rollers is adjusted to 115um, the rotating speed is 30rmp, the speed of the feeding pipe 6 is 10mL/min, the moving speed is 15cm/min, the two rollers are started after the feeding pipe 6 is opened for 7s, an ultraviolet light source is opened (the irradiation wavelength is 400nm, the power density is 120 w/cm), the two composite films are respectively transmitted into a pair of rotating rollers 7 of a roll-to-roll compounding machine, electrochromic layer gel is dripped between the two composite films through the feeding pipe 6, the two composite films are compounded through a roll-to-roll process, a wet film is prepared, the wet film is irradiated and solidified through an ultraviolet lamp 8, a dry film is formed, the device is taken down after film formation is completed, and the unfilled part of the electrochromic layer is cut off, so that the large-area electrochromic device is prepared.
Performance tests are carried out on the large-area electrochromic devices prepared in the examples 1-4, and the electrochromic devices are found to have high electrochemical contrast (68% -25% of contrast) and good stability, and the devices can still change color after 1000 cycles. In addition, the yield of the electrochromic device prepared according to the methods of examples 1-4 was above 93.4% (8.1% higher than that of the seven-layer electrochromic device prepared by the conventional method).
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. The preparation method of the large-area electrochromic device is characterized by comprising the following steps of:
(a) Mixing a polymer and a polymer dispersing agent, heating, stirring and dissolving to obtain a system A; adding electrolyte into the mixed solvent, and performing ultrasonic dissolution to obtain a system B; mixing the system A with the system B, adding a supporting material, ultrasonically mixing until the mixture is clear, and filtering to obtain a mixed system C;
the polymer is one or more of polyethylene, polyvinylidene fluoride, polyethylene oxide, polypropylene, polyacrylonitrile, polyacrylate, polymethyl methacrylate, polyvinyl alcohol, polyvinyl carbonate, polypropylene carbonate, polymethyl carbonate, polyethylene carbonate and polyurethane; the polymer dispersing agent is one or more of water, acetonitrile, methanol, ethanol, methylene dichloride, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene, paraxylene and ethyl acetate; the mass ratio of the polymer to the polymer dispersing agent is 1:2-1:10;
the electrolyte is one or more of lithium perchlorate, lithium tetrafluoroborate, ammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, lithium chloride, bis (trifluoromethanesulfonamide) lithium, 1-ethyl-3-methylimidazole trifluorophosphate, 1-butyl-3-methylimidazole trifluorophosphate, 1-ethyl-3-methylimidazole trifluorosulfonate, ferrocene, hydroquinone, potassium ferricyanide, 2, 6-tetramethylpiperidine, 2, 4-dimethoxy thiophene, tetramethyl p-phenylenediamine, p-phenylenediamine and p-methylaniline; the mixed solvent is at least two of deionized water, acetonitrile, methanol, ethanol, dichloromethane, 1, 2-dichloroethane, N-dimethylformamide, dimethyl sulfoxide, toluene and p-toluene; the dosage ratio of the electrolyte to the mixed solvent is (0.4-7) g: (20-160) mL; the mass ratio of the polymer to the electrolyte is 4-5: 1, a step of;
the supporting material is one or more of propylene acetate, propylene carbonate, ethylene carbonate, dimethyl carbonate and diethyl carbonate; the mass ratio of the polymer to the supporting material is 10:1-1:1;
(b) Adding the electrochromic material into the mixed system C, and performing ultrasonic or stirring dispersion until the electrochromic material is uniform to obtain a mixed system D; the mass ratio of the polymer to the electrochromic material in the step (a) is 50-150:1;
the electrochromic material is selected from one or more of materials shown in formulas (I), (II) and (III);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Is one or two of hydrogen, methyl, ethyl, acetyl, methoxy, acetamido, phenethyl, p-methylphenylethyl, 2, 4-dimethylphenylethyl, p-ethylphenyl ethyl and p-acetamido phenethyl, wherein X - Is chloride ion, bromide ion or hexafluorophosphate ion;
(c) Adding the photoinitiator into the mixed system D, carrying out light-shielding ultrasonic treatment or stirring and dispersing until the mixture is uniform, removing most of the mixed solvent by rotary evaporation, and distilling to remove all the solvent to obtain electrochromic layer gel;
the photoinitiator is one or more of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2-hydroxy-4' - (2-hydroxyethyl) -2-methyl propiophenone, phenyl-2, 4, 6-trimethylbenzoyl lithium phosphite and iodonium salt, and the mass ratio of electrochromic material to photoinitiator is (10-100) 1;
(d) And respectively conveying the two composite films into a pair of rotating rollers (7) of a roll-to-roll compounding machine, dripping the electrochromic layer gel between the two composite films through a feed pipe (6), compounding the two composite films through a roll-to-roll process, preparing a wet film with uniform thickness, and forming a dry film after the wet film is irradiated and solidified by an ultraviolet lamp (8), namely the electrochromic device.
2. The method of manufacturing a large area electrochromic device according to claim 1, wherein in step (a), the polymer is dissolved by stirring at 60-80 ℃.
3. The method of manufacturing a large area electrochromic device according to claim 1, wherein in step (c), the spin-steaming temperature is 60-100 ℃, the pressure is-0.05-0.2 MPaG, the time is 1-5 hours, and 70-98 wt% of the solvent is distilled out.
4. The method of manufacturing a large area electrochromic device according to claim 1, wherein in step (c), the distillation temperature is 70-130 ℃, the pressure is-0.1-0.8 mpa g, the time is 0.1-1 h, and the solvent content after evaporation is less than 0.05wt%.
5. A method of manufacturing a large area electrochromic device according to claim 1, characterized in that in step (d) the feed tube (6) is movable back and forth along the twin roll gap axis; the rotation speeds of the two rollers are the same, the rotation directions are opposite, and the rotation speed is 10-100 rpm; the gap between the two rollers is adjustable, and the adjustable range is 10 um-300 um.
6. The method of manufacturing a large area electrochromic device according to claim 1, wherein in step (d), the irradiation wavelength of the ultraviolet lamp (8) is 200 nm-400 nm, and the power density is 10-120 w/cm.
7. The method of claim 1, wherein in step (d), the wet film has a thickness of 20 to 200um and the dry film has a thickness of 15 to 200um.
8. The method of manufacturing a large area electrochromic device according to claim 1, wherein in step (d), the composite film is formed by compounding a film made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene, and transparent polyimide with an indium tin oxide electrode layer or fluorine doped tin oxide electrode layer or a silver nanowire electrode layer.
9. A large-area electrochromic device prepared by the method according to any one of claims 1 to 8, which is characterized by comprising a first transparent supporting layer (1), a first transparent conductive electrode layer (2), an electrochromic layer (3), a second transparent conductive electrode layer (4) and a second transparent supporting layer (5) which are stacked from top to bottom, wherein the first transparent supporting layer (1) and the second transparent supporting layer (5) are films made of one or two materials of glass, polybutylene terephthalate, polyethylene terephthalate, polyurethane, transparent polyethylene, transparent polypropylene and transparent polyimide; the first transparent conductive electrode layer (2) and the second transparent conductive electrode layer (4) are indium tin oxide electrode layers or fluorine-doped tin oxide electrode layers or silver nanowire electrode layers.
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Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060203322A1 (en) * | 2005-03-01 | 2006-09-14 | Bijan Radmard | Gel polymers containing ionic liquids |
| US20110233532A1 (en) * | 2010-03-25 | 2011-09-29 | Sotzing Gregory A | Formation of conjugated polymers for solid-state devices |
| CN103992434A (en) * | 2014-04-23 | 2014-08-20 | 宁波祢若电子科技有限公司 | Ultraviolet-curable electrolyte gel and its application in electrochromic device |
| CN105954954A (en) * | 2016-06-23 | 2016-09-21 | 上海师范大学 | Solid-state electrochromic device and preparation method and application thereof |
| CN106291996A (en) * | 2015-05-26 | 2017-01-04 | 北京生美鸿业科技有限公司 | The volume to volume preparation method of Graphene compound transparent electricity conductive film and intelligent light modulation film |
| CN108897179A (en) * | 2018-06-14 | 2018-11-27 | 盐城易快来科技有限公司 | A kind of photocuring electrolyte, electrochromic device and preparation method thereof |
| CN109107399A (en) * | 2018-07-30 | 2019-01-01 | 绍兴百立盛新材料科技有限公司 | A kind of hydrone permeable membrane and its preparation method and application |
| CN109212859A (en) * | 2018-10-12 | 2019-01-15 | 上海洞舟实业有限公司 | A kind of elastically stretchable electrochromic device |
| CN109856882A (en) * | 2019-03-25 | 2019-06-07 | 华南理工大学 | A kind of electrochomeric glass and its packaging method |
| CN110716360A (en) * | 2019-09-24 | 2020-01-21 | 浙江工业大学 | A high-performance all-solid-state polymer electrochromic device and preparation method thereof |
| CN110928095A (en) * | 2019-11-14 | 2020-03-27 | 浙江工业大学 | Dual electrochromic layer device capable of realizing conversion between any colors and assembling method |
| CN112415826A (en) * | 2020-11-18 | 2021-02-26 | 浙江大学 | A simple and efficient method for preparing multicolor all-solid-state electrochromic devices |
| CN112666771A (en) * | 2020-12-25 | 2021-04-16 | 广州熵能创新材料股份有限公司 | Electrochromic assembly and electrochromic device prepared by same |
| CN113050338A (en) * | 2021-03-16 | 2021-06-29 | 宁波伯宇科技有限公司 | Electrochromic device manufacturing process |
| CN113741111A (en) * | 2021-08-06 | 2021-12-03 | 浙江工业大学 | Integrated electrochromic device and preparation method thereof |
| CN115963666A (en) * | 2021-10-12 | 2023-04-14 | 南京林业大学 | A highly stable hydrogel electrolyte for electrochromic devices |
| CN116731240A (en) * | 2022-03-04 | 2023-09-12 | 海信视像科技股份有限公司 | Electrolyte solution, electrochromic device and preparation method of electrochromic device |
| CN116909067A (en) * | 2023-07-18 | 2023-10-20 | 浙江工业大学 | A transparent-black light-curing electrochromic device and its preparation method and application |
| CN117111368A (en) * | 2023-08-11 | 2023-11-24 | 浙江工业大学 | Electrochromic display device without ion storage layer and preparation method thereof |
-
2023
- 2023-12-26 CN CN202311804770.7A patent/CN117799197A/en active Pending
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060203322A1 (en) * | 2005-03-01 | 2006-09-14 | Bijan Radmard | Gel polymers containing ionic liquids |
| US20110233532A1 (en) * | 2010-03-25 | 2011-09-29 | Sotzing Gregory A | Formation of conjugated polymers for solid-state devices |
| CN103992434A (en) * | 2014-04-23 | 2014-08-20 | 宁波祢若电子科技有限公司 | Ultraviolet-curable electrolyte gel and its application in electrochromic device |
| CN106291996A (en) * | 2015-05-26 | 2017-01-04 | 北京生美鸿业科技有限公司 | The volume to volume preparation method of Graphene compound transparent electricity conductive film and intelligent light modulation film |
| CN105954954A (en) * | 2016-06-23 | 2016-09-21 | 上海师范大学 | Solid-state electrochromic device and preparation method and application thereof |
| CN108897179A (en) * | 2018-06-14 | 2018-11-27 | 盐城易快来科技有限公司 | A kind of photocuring electrolyte, electrochromic device and preparation method thereof |
| CN109107399A (en) * | 2018-07-30 | 2019-01-01 | 绍兴百立盛新材料科技有限公司 | A kind of hydrone permeable membrane and its preparation method and application |
| CN109212859A (en) * | 2018-10-12 | 2019-01-15 | 上海洞舟实业有限公司 | A kind of elastically stretchable electrochromic device |
| CN109856882A (en) * | 2019-03-25 | 2019-06-07 | 华南理工大学 | A kind of electrochomeric glass and its packaging method |
| CN110716360A (en) * | 2019-09-24 | 2020-01-21 | 浙江工业大学 | A high-performance all-solid-state polymer electrochromic device and preparation method thereof |
| CN110928095A (en) * | 2019-11-14 | 2020-03-27 | 浙江工业大学 | Dual electrochromic layer device capable of realizing conversion between any colors and assembling method |
| CN112415826A (en) * | 2020-11-18 | 2021-02-26 | 浙江大学 | A simple and efficient method for preparing multicolor all-solid-state electrochromic devices |
| CN112666771A (en) * | 2020-12-25 | 2021-04-16 | 广州熵能创新材料股份有限公司 | Electrochromic assembly and electrochromic device prepared by same |
| CN113050338A (en) * | 2021-03-16 | 2021-06-29 | 宁波伯宇科技有限公司 | Electrochromic device manufacturing process |
| CN113741111A (en) * | 2021-08-06 | 2021-12-03 | 浙江工业大学 | Integrated electrochromic device and preparation method thereof |
| CN115963666A (en) * | 2021-10-12 | 2023-04-14 | 南京林业大学 | A highly stable hydrogel electrolyte for electrochromic devices |
| CN116731240A (en) * | 2022-03-04 | 2023-09-12 | 海信视像科技股份有限公司 | Electrolyte solution, electrochromic device and preparation method of electrochromic device |
| CN116909067A (en) * | 2023-07-18 | 2023-10-20 | 浙江工业大学 | A transparent-black light-curing electrochromic device and its preparation method and application |
| CN117111368A (en) * | 2023-08-11 | 2023-11-24 | 浙江工业大学 | Electrochromic display device without ion storage layer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王猛等: "《手印显现技术前沿》", 31 August 2019, pages: 196 - 197 * |
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