CN105372896A - Preparation of solid electrolyte electrochromic flexible device based on conductive polymer - Google Patents
Preparation of solid electrolyte electrochromic flexible device based on conductive polymer Download PDFInfo
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- CN105372896A CN105372896A CN201510810819.9A CN201510810819A CN105372896A CN 105372896 A CN105372896 A CN 105372896A CN 201510810819 A CN201510810819 A CN 201510810819A CN 105372896 A CN105372896 A CN 105372896A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000007787 solid Substances 0.000 claims abstract description 29
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 239000002356 single layer Substances 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 37
- 239000003115 supporting electrolyte Substances 0.000 claims description 33
- 238000004528 spin coating Methods 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 27
- 239000008151 electrolyte solution Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 22
- 239000002322 conducting polymer Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 229920002521 macromolecule Polymers 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- -1 allyl ester Chemical class 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical group [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229920000767 polyaniline Polymers 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- DYVIVMCAMDJZLM-UHFFFAOYSA-N C(F)(F)F.C(CCC)N1CN(C=C1)C Chemical compound C(F)(F)F.C(CCC)N1CN(C=C1)C DYVIVMCAMDJZLM-UHFFFAOYSA-N 0.000 claims description 8
- RAFKCLFWELPONH-UHFFFAOYSA-N acetonitrile;dichloromethane Chemical group CC#N.ClCCl RAFKCLFWELPONH-UHFFFAOYSA-N 0.000 claims description 8
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical group [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000003446 memory effect Effects 0.000 abstract 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 22
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 238000013461 design Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000004984 smart glass Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001716 carbazoles Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- PLXMOAALOJOTIY-FPTXNFDTSA-N Aesculin Natural products OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)[C@H]1Oc2cc3C=CC(=O)Oc3cc2O PLXMOAALOJOTIY-FPTXNFDTSA-N 0.000 description 1
- 241000139306 Platt Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
-
- 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
-
- 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
- G02F2001/164—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 the electrolyte is made of polymers
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention provides a preparation method of a solid electrolyte electrochromic flexible device based on a conductive polymer, which comprises the following steps: preparing a solid electrolyte, preparing a positive electrode material, preparing a negative electrode material, and assembling a single-layer solid device; in the invention, the adopted solid electrolyte is independently designed and prepared in a laboratory, the preparation method is simple and convenient, and the environmental stability is good; compared with inorganic and organic micromolecules, the adopted conductive polymer electrochromic material has the advantages of multiple structural types, wide color change range, high optical contrast, good processing performance, high response speed and the like; the conductive polymer-based solid device film has electrochromic performance, so the conductive polymer-based solid device film has great application prospect in the fields of displays, intelligent windows, electronic paper and the like; the electrochromic material has the advantages of low driving voltage, color memory effect and the like, so that the electrochromic material has a remarkable electricity-saving effect, and passive light emission is more favorable for protecting human eyes.
Description
(1) technical field
The present invention relates to a kind of preparation method of electrochromic device, be specifically related to a kind of preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer.
(2) background technology
Electrochromism phenomenon refers under DC Electric Field, due to injection or the extraction of redox reaction or electric charge (electronics or ion), (comprising transmissivity, absorptivity and reflectivity etc.) there is reversible transformation in the optical property of material, its macro manifestations is that the color of material possesses reversible transformation with DC Electric Field in visible wavelength range.Since nineteen sixties Platt proposes electrochromism concept, electrochromic material causes people's extensive concern.Different according to the structure of material, inorganic electrochromic material and organic electrochromic material can be divided into.Early stage research work mainly concentrates on inorganic electrochromic material, comprises transition metal oxide, as tungstic acid (WO
3), iridium dioxide (IrO
2), Prussian blue system etc.Inorganic electrochromic material has good photochemical stability, but its processability, color plasticity are strong, coloration efficiency is not high, limits its large-scale application in productive life.And organic molecule and conductive polymers based electrochromic material (comprise viologen organic micromolecule, polypyrrole, polythiophene, polyaniline, poly-indoles, the poly-conducting polymer such as furans and corresponding derivative) deficiency of inorganic electrochromic material can be made up, be subject to people's attention gradually.Wherein conducting polymer electrochromic material has that structure species is many, color change interval is wide, optical contrast is high, the advantage such as good processability and fast response time, being considered to one of developing direction of electrochromism of future generation (EC) material, providing good material foundation for developing the high performance electrochromism solid state device of preparation further.
At Material Field, the electrochromic device positive pole many employings inorganic electrochromic material existed in the market, these materials only have the conversion between single coloured state and clear state or two kinds of colors usually, transition response is slow, usually tens seconds to be reached, and optical contrast is not high, be therefore difficult to the requirement meeting high-end electrochromic device.Organic molecule EC material color enriches, and the response time is also than comparatively fast, but stability is very poor, is difficult to the Long-Time Service ensureing device.And polymer electrochromic material, can be realized the display of multiple different colours by the means such as structural design and copolymerization of monomer, response speed is much better than traditional inorganic electrochromic material, and stability has larger improvement than organic molecule.
And in device electrolyte, electrolyte main is at present the electrolyte of liquid electrolyte or for dense fluids shape, although this kind of electrolyte conductivity is pretty good, but electrochemical stability is poor, high to encapsulation conditional request, be easy to leakage, once leakage and long-term to place environmental stability also very poor, cause serviceable life low, at present the general transparency of solid electrolyte of research is all very poor, therefore finds a kind of high conductivity and the high solid electrolyte of transmissivity is extremely urgent.
At present, what the display devices such as display market existed, Electronic Paper, electric advertisement screen adopted mostly is liquid crystal or electrophoretic techniques.Liquid crystal power consumption is large, opaque and cannot realize Flexible Displays; Electrophoresis can only show transparent with opaque or fixing several colors usually.The present invention prepare based on conducting polymer electrochromic material monolayer solid device, no matter choose at functional material, all embody obvious advantage in stable, color, the energy consumption etc. of device, for high-performance conductive polymer electrochromic material solid device is at display device, smart window, the technical fields such as automobile rearview mirror lay good basis.
But conducting polymer electrochromic material does not also have large area commercial application, the domestic producer that there is no PEC material and solid state device large-scale production thereof even at present in fields such as display technique, smart window, auto industrys at present.Main cause have following some: the first, the technology of preparing of the PEC material of high-performance and low-cost is ripe not enough, and basic theory is also perfect not; Design and the assembling second, with the PEC material solid device of excellent properties are also in design development, mainly contain a difficult problem for three aspects: (1) high performance solid electrolyte, (2) high performance electrode material, the appropriate design of (3) solid state device and package technique.The present invention mainly prepares in the novelty of solid electrolyte material, and the package technique aspect of device is explored, and has successfully prepared the conducting polymer electrochromic material solid state device with polychrome, response fast.
(3) summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of technique is simple, with low cost, the preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer of stable performance, and the technical matters mainly solved is the preparation of solid electrolyte and the assembling of solid state device.
The preparation method of a kind of solid electrolyte electrochromism flexible device based on conducting polymer of the present invention mainly comprises: the design of the preparation of positive and negative electrode electrode material, the preparation of solid electrolyte, device architecture, device assembling.
The present invention adopts following technical scheme:
Based on a preparation method for the solid electrolyte electrochromism flexible device of conducting polymer, described preparation method comprises the steps:
(1) preparation of solid electrolyte: by polymeric plasticizer and the mixing of macromolecule sweller, the baking oven being placed in 50 ~ 80 DEG C heats swelling 10 ~ 24h, is designated as system A; Supporting electrolyte X, doping electrolyte and electroanalysis solvent X are mixed, in the ultrasonic 2 ~ 10h of 50 ~ 100KHz, is designated as system B; Described system A to be mixed with system B, and by gained potpourri in the ultrasonic 2 ~ 10h of 50 ~ 100KHz, be placed in 70 ~ 90 DEG C of vacuum drying chambers and leave standstill 5 ~ 15h, obtain described solid electrolyte;
In step (1), described polymeric plasticizer is polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF) or poly-(vinylidene fluoride-hexachloropropylene) (PVDF-HFP), preferably polymethylmethacrylate (PMMA);
Described macromolecule sweller is carbonic allyl ester (PC) or polyglycol, is preferably carbonic allyl ester (PC);
Described supporting electrolyte X is tetrabutylammonium perchlorate, lithium perchlorate, 4-butyl ammonium fluoroborate or LiBF4, is preferably LiBF4;
Described doping electrolyte is two (fluoroform sulphonyl) inferior amine salt of 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole fluoroform sulphonate or 1-butyl-3-methylimidazole, is preferably 1-butyl-3-methylimidazole fluoroform sulphonate;
Described electroanalysis solvent X is acetonitrile, methylene chloride, isopropyl alcohol or acetonitrile-dichloromethane mixed solvent, is preferably the mixed solvent of acetonitrile-dichloromethane volume ratio 3:7;
In described system A, the mass ratio of polymeric plasticizer and macromolecule sweller is 1:1.5 ~ 4; In described system B, the mass ratio of supporting electrolyte X, doping electrolyte and electroanalysis solvent X is 1:2 ~ 5:5 ~ 30; The mass ratio of described system A and system B is 1:0.22 ~ 1.97.
(2) preparation of positive electrode: electroanalysis solvent A, monomer A and supporting electrolyte A are hybridly prepared into electrolytic solution and add in three-electrode cell, under 0.7 ~ 1.52V condition, adopt potentiostatic method to carry out polyreaction, terminate when being polymerized polymerization when consumes power reaches 0.01 ~ 0.15C, be-0.2 ~-1.2V by control of Electric potentials, dedoping process 100 ~ 300s is carried out to the working electrode after polyreaction, with the working electrode after electrolysis solvent orange 2 A cleaning dedoping, put into 50 ~ 80 DEG C of vacuum drying chambers afterwards and dry 5 ~ 10h, obtain described positive electrode;
In step (2), described three-electrode cell take conductive substrates as working electrode, is preferably ITO (tin indium oxide) glass electrode, ITO-PET (being coated with the pet material of conductive indium-tin oxide layer) flexible electrode; With gold or platinum electrode for auxiliary electrode, be preferably platinum electrode; With mercurous chloride electrode or silver-silver chloride electrode for contrast electrode, be preferably silver-silver chloride electrode;
Described electroanalysis solvent A is acetonitrile, methylene chloride, acetonitrile-dichloromethane mixed liquor or deionized water, is preferably deionized water;
Described monomer A is thiophene-based, triphen amine or carbazoles organic molecule, and be specially aniline or TBTPA (triphenylamine coupling thiophene), described monomer A initial concentration is in the electrolytic solution 0.01 ~ 0.6mol/L;
Described supporting electrolyte A is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, and be preferably sulfuric acid, described supporting electrolyte A concentration is in the electrolytic solution 0.01 ~ 5mol/L;
The positive electrode of gained is the conductive substrates depositing thin polymer film;
(3) preparation of negative material: electroanalysis solvent B, monomers B and supporting electrolyte B are hybridly prepared into electrolytic solution and add in three-electrode cell, under 0.7 ~ 1.52V condition, adopt potentiostatic method to carry out polyreaction, terminate when being polymerized polymerization when consumes power reaches 0.01 ~ 0.15C, be-0.2 ~-0.6V by control of Electric potentials, dedoping process 100 ~ 300s is carried out to the working electrode after polyreaction, the working electrode after dedoping is cleaned with electroanalysis solvent B, put into 50 ~ 80 DEG C of vacuum drying chambers afterwards and dry 5 ~ 10h, obtain described negative material;
In step (3), described three-electrode cell take conductive substrates as working electrode, is preferably ITO (tin indium oxide) glass electrode, ITO-PET (being coated with the pet material of conductive indium-tin oxide layer) flexible electrode; With gold or platinum electrode for auxiliary electrode, be preferably platinum electrode; With mercurous chloride electrode or silver-silver chloride electrode for contrast electrode, be preferably silver-silver chloride electrode;
Described electroanalysis solvent B is acetonitrile, methylene chloride, acetonitrile-dichloromethane mixed liquor or deionized water, is preferably the mixed liquor of acetonitrile-dichloromethane volume ratio 1:2 ~ 5;
Described monomers B is thiophene-based, triphen amine, carbazoles organic molecule, is specially EDOT (3,4-rthylene dioxythiophene), and described monomers B initial concentration is in the electrolytic solution 0.002 ~ 0.1mol/L;
Described supporting electrolyte B is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, and be preferably tetrabutylammonium perchlorate, described supporting electrolyte B concentration is in the electrolytic solution 0.01 ~ 1mol/L;
The negative material of gained is the conductive substrates depositing thin polymer film;
(4) assembling of monolayer solid device: the solid electrolyte that step (1) is obtained is laid on the obtained positive electrode of step (2), then the negative material that step (3) is obtained is covered above solid electrolyte, obtain the material with three-layer sandwich structure, be placed in 40 ~ 70 DEG C of baking ovens and heat 3 ~ 7h (in this heating process, hand extrusion device can be used every half an hour, positive and negative electrode material and solid electrolyte are enough bonded), obtain the described solid electrolyte electrochromism flexible device based on conducting polymer.
In the present invention, described positive electrode is also prepared by following spin-coating method:
By polymer electrochromic material dissolves in a solvent, obtain the solution of polymer electrochromic material, drip above-mentioned solution on a flexible substrate, make it to cover flexible substrates completely, leave standstill 2 ~ 15min, then open spin coating instrument and be divided into three phases and carry out spin coating:
First stage: be 300 ~ 700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution;
Subordinate phase: first grade: be 300 ~ 700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution; Second gear: be 1300 ~ 1700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution equally;
Phase III: repeat the process of subordinate phase, finally drying at room temperature under nitrogen protection, obtain described positive electrode;
Described polymer electrochromic material is polyaniline;
Described solvent is 1-Methyl-2-Pyrrolidone;
In the solution of described polymer electrochromic material, the concentration of polymer electrochromic material is 0.01 ~ 0.03g/mL;
Described flexible substrates is ITO-PET (being coated with the pet material of conductive indium-tin oxide layer).
Described spin-coating method is prepared in the process of positive electrode, and preferred first stage spin coating instrument rotating speed is 500 revs/min, and the time is 3min;
In second and third stage, preferably first grade of spin coating instrument rotating speed is 500 revs/min, and the time is 3min; Preferred second gear spin coating instrument rotating speed is 1500 revs/min, and the time is 3min.
In the present invention, term " system A ", " system B " do not have special implication, are labeled as " A ", " B " just for distinguishing different systems.Term " supporting electrolyte X ", " supporting electrolyte A ", " supporting electrolyte B " do not have special implication yet, be labeled as " X ", " A ", " B " just for distinguishing the supporting electrolyte used in different step, " electroanalysis solvent X ", " electroanalysis solvent A ", " electroanalysis solvent B ", " monomer A ", " monomers B " are with it in like manner.
The present invention is characterized gained solid state device by cyclic voltammetry, confirms that solid state device has electrochromic property, namely can realize different color changes in certain voltage range; Tested by many potential step methods, confirm that monolayer solid device has the performance of quick color change, and carried out the test of response speed to device, confirming that its response speed is very fast, is a kind of device of electrochromic property excellence.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) solid electrolyte adopted in the present invention is laboratory autonomous Design preparation, and preparation method is easy, and environmental stability is good, and does not need harsh reaction conditions, just can operate under room temperature;
(2) the conducting polymer electrochromic material that adopts of the present invention, compares with organic molecule with inorganic, has that structure species is many, color change interval is wide, optical contrast is high, the advantage such as good processability and fast response time;
(3) the present invention's conductive polymers based solid state device film has electrochromic performance, thus has huge application prospect in fields such as display, smart window, Electronic Paper;
(4) electrochromic material of the present invention has the advantages such as driving voltage is low, memory for color effect, its power saving effect is given prominence to, and passive luminescence is more conducive to the protection of human eye.
(4) accompanying drawing explanation
Fig. 1 a, 1b be the flexible solid device of assembling in embodiment 1 in energising (0.9V, Fig. 1 a) and the diagram of (0V, Fig. 1 b) of not being energized down;
Fig. 2 a, 2b are that the flexible solid device of assembling in embodiment 2 is in energising (0.9V, Fig. 2 diagram a) and under be not energized (0V, Fig. 2 b);
Fig. 3 a, 3b are that the flexible solid device of assembling in embodiment 3 is in energising (0.9V, Fig. 3 diagram a) and under be not energized (0V, Fig. 3 b);
Fig. 4 a, 4b are that the flexible solid device of assembling in embodiment 4 is in energising (0.9V, Fig. 4 diagram a) and under be not energized (0V, Fig. 4 b).
(5) embodiment
With specific embodiment, technical scheme of the present invention is further described below, but protection scope of the present invention is not limited thereto.
Embodiment 1
Based on a preparation method for the solid electrolyte electrochromism flexible device of conducting polymer, comprise the following steps:
(1) solid electrolyte is prepared: added by polymeric plasticizer PMMA1.75g and macromolecule sweller PC5g in the round-bottomed flask or reagent bottle with a lid being with hollow plug, the baking oven being placed in 70 DEG C heats swelling 12h, make good swelling in macromolecule sweller of macromolecule transparent material, be designated as system A.By supporting electrolyte LiBF
40.24g and doping electrolyte 1-butyl-3-methylimidazole fluoroform sulphonate 0.8g and electroanalysis solvent (acetonitrile 3g-methylene chloride 0.75g) add in round-bottomed flask, uncoveredly be placed in the ultrasonic 5h in the ultrasonic pond of 80KHz, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent, be designated as system B.System A, system B are poured in the round-bottomed flask of same band hollow plug or reagent bottle with a lid and mix, potpourri is in the ultrasonic 7h of 80KHz afterwards, potpourri is made to present gel, pour into afterwards in double dish, and the double dish that potpourri is housed is put into vacuum drying chamber (82 DEG C), place 10h, the electrolyte finally obtained is flexible solid shape, somewhat viscous, thickness is 0.8mm.
(2) positive electrode is prepared: monomer A is aniline, and its structure is as follows:
By monomer aniline 2.328g and 98% sulfuric acid 5g, Homogeneous phase mixing in 50ml volumetric flask is mixed with electrolytic solution (solvent is deionized water), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 0.7V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.06C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, be-0.2V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then the working electrode after washed with de-ionized water dedoping is used, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain positive electrode (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(3) negative material is prepared: monomers B is EDOT, monomer 0.355g and tetrabutylammonium perchlorate 1.71g Homogeneous phase mixing in 50ml volumetric flask is mixed with electrolytic solution (solvent is acetonitrile), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 1.4V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.04C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, when being-0.6V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then with the working electrode after acetonitrile cleaning dedoping, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain negative material (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(4) assembly device: the solid electrolyte that step (1) is obtained is cut into the identical square of the positive electrode useful area size obtained with step (2), be laid on positive electrode, afterwards by negative material lid obtained for step (3) side on the solid electrolyte, use have gentle hands pressure, put and heat 6h (temperature 60 C) in an oven, hand extrusion device is used every half an hour, ensure that positive and negative electrode material and solid electrolyte enough bond, obtain described device.
(5) performance test: the solid state device electrochemical workstation of gained in step (4) is tested, can be observed the reversible change that device color there occurs blackish green-green color-blue in cyclic voltammetry scan process.Fig. 1 a, 1b be device obtained in step (4) "on" position (0.9V, Fig. 1 a) under and color under (0V, Fig. 1 b) state that is not energized.
Embodiment 2
(1) solid electrolyte is prepared: added by polymeric plasticizer PMMA1.75g and macromolecule sweller PC3g in the round-bottomed flask or reagent bottle with a lid being with hollow plug, the baking oven being placed in 70 DEG C heats swelling 12h, make good swelling in macromolecule sweller of macromolecule transparent material, be designated as system A.By supporting electrolyte LiBF
40.14g and doping electrolyte 1-butyl-3-methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g-methylene chloride 0.75g) add in round-bottomed flask, uncoveredly be placed in the ultrasonic 5h in the ultrasonic pond of 80KHz, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent, be designated as system B.System A, system B are poured in the round-bottomed flask of same band hollow plug or reagent bottle with a lid and mix, potpourri is in the ultrasonic 7h of 80KHz afterwards, potpourri is made to present gel, pour into afterwards in double dish, and the double dish that potpourri is housed is put into vacuum drying chamber (82 DEG C), place 10h, the electrolyte finally obtained is flexible solid shape, somewhat viscous, thickness is 0.8mm.
(2) positive electrode is prepared: monomer A is aniline, monomer aniline 2.328g and 98% sulfuric acid 5g Homogeneous phase mixing in 50ml volumetric flask are mixed with electrolytic solution (solvent is deionized water), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 0.7V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.06C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, be-0.2V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then the working electrode after washed with de-ionized water dedoping is used, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain positive electrode (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(3) negative material is prepared: monomers B is EDOT, monomer 0.355g and tetrabutylammonium perchlorate 1.71g Homogeneous phase mixing in 50ml volumetric flask is mixed with electrolytic solution (solvent is acetonitrile), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 1.4V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.04C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, when being-0.6V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then with the working electrode after acetonitrile cleaning dedoping, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain negative material (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(4) assembly device: the solid electrolyte that step (1) is obtained is cut into the identical square of the positive electrode useful area size obtained with step (2), be laid on positive electrode, afterwards by negative material lid obtained for step (3) side on the solid electrolyte, use have gentle hands pressure, put and heat 6h (temperature 60 C) in an oven, hand extrusion device is used every half an hour, ensure that positive and negative electrode material and solid electrolyte enough bond, obtain described device.
(5) performance test: the solid state device electrochemical workstation of gained in step (4) is tested, can be observed the reversible change that device color there occurs blackish green-green color-blue in cyclic voltammetry scan process.Fig. 2 a, 2b be device obtained in step (4) "on" position (0.9V, Fig. 2 a) under and color under (0V, Fig. 2 b) state that is not energized.
Embodiment 3
(1) solid electrolyte is prepared: added by polymeric plasticizer PMMA1.75g and macromolecule sweller PC3g in the round-bottomed flask or reagent bottle with a lid being with hollow plug, the baking oven being placed in 70 DEG C heats swelling 12h, make good swelling in macromolecule sweller of macromolecule transparent material, be designated as system A.By supporting electrolyte LiBF
40.14g and doping electrolyte 1-butyl-3-methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g-methylene chloride 0.75g) add in round-bottomed flask, uncoveredly be placed in the ultrasonic 5h in the ultrasonic pond of 80KHz, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent, be designated as system B.System A, system B are poured in the round-bottomed flask of same band hollow plug or reagent bottle with a lid and mix, potpourri is in the ultrasonic 7h of 80KHz afterwards, potpourri is made to present gel, pour into afterwards in double dish, and the double dish that potpourri is housed is put into vacuum drying chamber (82 DEG C), place 10h, the electrolyte finally obtained is flexible solid shape, somewhat viscous, thickness is 0.88mm.
(2) positive electrode (spin-coating method) is prepared: be dissolved in by polyaniline 5g in 250mL nitrogen methyl pyrrolidone, obtain polyaniline solutions, be poured in conical flask, spin coating is carried out afterwards by spin coating instrument, first on flexible substrates ITO-PET, 3 above-mentioned polyaniline solutions are dripped, make it to cover flexible substrates completely, leave standstill 2 minutes, start spin coating instrument spin coating three times afterwards: be 1. 700 revs/min by rotational speed regulation, set of time is 2min, turn while drip solution, 2. first grade: be 700 revs/min by rotational speed regulation, set of time is 2min, second gear: be 1500 revs/min by rotational speed regulation, set of time is 2min.To turn while drip solution equally.3. 2. step is repeated, finally dry under nitrogen protection room temperature, obtain positive electrode.
(3) negative material is prepared: monomers B is EDOT, monomer 0.355g and tetrabutylammonium perchlorate 1.71g Homogeneous phase mixing in 50ml volumetric flask is mixed with electrolytic solution (solvent is acetonitrile), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 1.4V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.04C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, when being-0.6V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then with the working electrode after acetonitrile cleaning dedoping, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain negative material (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(4) assembly device: the solid electrolyte that step (1) is obtained is cut into the identical square of the positive electrode useful area size obtained with step (2), be laid on positive electrode, afterwards by negative material lid obtained for step (3) side on the solid electrolyte, use have gentle hands pressure, put and heat 6h (temperature 60 C) in an oven, hand extrusion device is used every half an hour, ensure that positive and negative electrode material and solid electrolyte enough bond, obtain described device.
(5) performance test: the solid state device electrochemical workstation of gained in step (4) is tested, can be observed the reversible change that device color there occurs blackish green-green color-blue in cyclic voltammetry scan process.Fig. 3 a, 3b be device obtained in step (4) "on" position (0.9V, Fig. 3 a) under and color under (0V, Fig. 3 b) state that is not energized.
Embodiment 4
(1) solid electrolyte is prepared: added by polymeric plasticizer PMMA1.75g and macromolecule sweller PC3g in the round-bottomed flask or reagent bottle with a lid being with hollow plug, the baking oven being placed in 70 DEG C heats swelling 12h, make good swelling in macromolecule sweller of macromolecule transparent material, be designated as system A.By supporting electrolyte LiBF
40.14g and doping electrolyte 1-butyl-3-methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g-methylene chloride 0.75g) add in round-bottomed flask, uncoveredly be placed in the ultrasonic 5h in the ultrasonic pond of 80KHz, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent, be designated as system B.System A, system B are poured in the round-bottomed flask of same band hollow plug or reagent bottle with a lid and mix, potpourri is in the ultrasonic 7h of 80KHz afterwards, potpourri is made to present gel, pour into afterwards in double dish, and the double dish that potpourri is housed is put into vacuum drying chamber (82 DEG C), place 10h, the electrolyte finally obtained is flexible solid shape, somewhat viscous, thickness is 0.88mm.
(2) positive electrode (spin-coating method) is prepared: be dissolved in by polyaniline 5g in 250mL nitrogen methyl pyrrolidone, obtain polyaniline solutions, be poured in conical flask, spin coating is carried out afterwards by spin coating instrument, first on flexible substrates ITO-PET, 3 above-mentioned polyaniline solutions are dripped, make it to cover flexible substrates completely, leave standstill 5 minutes, start spin coating instrument spin coating three times afterwards: be 1. 500 revs/min by rotational speed regulation, set of time is 3min, turn while drip solution, 2. first grade: be 500 revs/min by rotational speed regulation, set of time is 3min, second gear: be 1500 revs/min by rotational speed regulation, set of time is 3min.To turn while drip solution equally.3. 2. step is repeated, finally dry under nitrogen protection room temperature, obtain positive electrode.
(3) negative material is prepared: monomers B is EDOT, monomer 0.355g and tetrabutylammonium perchlorate 1.71g Homogeneous phase mixing in 50ml volumetric flask is mixed with electrolytic solution (solvent is acetonitrile), then electrolytic solution is joined in three-electrode cell, wherein working electrode is ITO conductive glass electrode (it is of a size of 2cm × 2cm), auxiliary electrode is platinum electrode, and contrast electrode is silver-silver chloride electrode.Under polymerization current potential 1.4V condition, adopt potentiostatic method to carry out polyreaction, when polymerization consumes power reaches 0.04C, polymerization terminates, working electrode ITO conductive glass surface deposited the polymer film of blue layer, when being-0.6V by control of Electric potentials, dedoping process 100s is carried out to the working electrode after polyreaction, then with the working electrode after acetonitrile cleaning dedoping, put into 70 DEG C of vacuum drying chambers and dry 7h, obtain negative material (depositing the ITO conductive glass electrode of conducting polymer thin film) stand-by.
(4) assembly device: the solid electrolyte that step (1) is obtained is cut into the identical square of the positive electrode useful area size obtained with step (2), be laid on positive electrode, afterwards by negative material lid obtained for step (3) side on the solid electrolyte, use have gentle hands pressure, put and heat 6h (temperature 60 C) in an oven, hand extrusion device is used every half an hour, ensure that positive and negative electrode material and solid electrolyte enough bond, obtain described device.
(5) performance test: the solid state device electrochemical workstation of gained in step (4) is tested, can be observed the reversible change that device color there occurs blackish green-green color-blue in cyclic voltammetry scan process.Fig. 4 a, 4b be device obtained in step (4) "on" position (0.9V, Fig. 4 a) under and color under (0V, Fig. 4 b) state that is not energized.
Claims (10)
1., based on a preparation method for the solid electrolyte electrochromism flexible device of conducting polymer, it is characterized in that, described preparation method comprises the steps:
(1) preparation of solid electrolyte: by polymeric plasticizer and the mixing of macromolecule sweller, the baking oven being placed in 50 ~ 80 DEG C heats swelling 10 ~ 24h, is designated as system A; Supporting electrolyte X, doping electrolyte and electroanalysis solvent X are mixed, in the ultrasonic 2 ~ 10h of 50 ~ 100KHz, is designated as system B; Described system A to be mixed with system B, and by gained potpourri in the ultrasonic 2 ~ 10h of 50 ~ 100KHz, be placed in 70 ~ 90 DEG C of vacuum drying chambers and leave standstill 5 ~ 15h, obtain described solid electrolyte;
In step (1), described polymeric plasticizer is polymethylmethacrylate, polyvinylidene fluoride or poly-(vinylidene fluoride-hexachloropropylene);
Described macromolecule sweller is carbonic allyl ester or polyglycol;
Described supporting electrolyte X is tetrabutylammonium perchlorate, lithium perchlorate, 4-butyl ammonium fluoroborate or LiBF4;
Described doping electrolyte is two (fluoroform sulphonyl) inferior amine salt of 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole fluoroform sulphonate or 1-butyl-3-methylimidazole;
Described electroanalysis solvent X is acetonitrile, methylene chloride, isopropyl alcohol or acetonitrile-dichloromethane mixed solvent;
In described system A, the mass ratio of polymeric plasticizer and macromolecule sweller is 1:1.5 ~ 4; In described system B, the mass ratio of supporting electrolyte X, doping electrolyte and electroanalysis solvent X is 1:2 ~ 5:5 ~ 30; The mass ratio of described system A and system B is 1:0.22 ~ 1.97.
(2) preparation of positive electrode: electroanalysis solvent A, monomer A and supporting electrolyte A are hybridly prepared into electrolytic solution and add in three-electrode cell, under 0.7 ~ 1.52V condition, adopt potentiostatic method to carry out polyreaction, terminate when being polymerized polymerization when consumes power reaches 0.01 ~ 0.15C, be-0.2 ~-1.2V by control of Electric potentials, dedoping process 100 ~ 300s is carried out to the working electrode after polyreaction, with the working electrode after electrolysis solvent orange 2 A cleaning dedoping, put into 50 ~ 80 DEG C of vacuum drying chambers afterwards and dry 5 ~ 10h, obtain described positive electrode;
In step (2), described three-electrode cell take conductive substrates as working electrode, and described conductive substrates is selected from ito glass electrode, ITO-PET flexible electrode; With gold or platinum electrode for auxiliary electrode; With mercurous chloride electrode or silver-silver chloride electrode for contrast electrode;
Described electroanalysis solvent A is acetonitrile, methylene chloride, acetonitrile-dichloromethane mixed liquor or deionized water;
Described monomer A is aniline or TBTPA, and described monomer A initial concentration is in the electrolytic solution 0.01 ~ 0.6mol/L;
Described supporting electrolyte A is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, and described supporting electrolyte A concentration is in the electrolytic solution 0.01 ~ 5mol/L;
(3) preparation of negative material: electroanalysis solvent B, monomers B and supporting electrolyte B are hybridly prepared into electrolytic solution and add in three-electrode cell, under 0.7 ~ 1.52V condition, adopt potentiostatic method to carry out polyreaction, terminate when being polymerized polymerization when consumes power reaches 0.01 ~ 0.15C, be-0.2 ~-0.6V by control of Electric potentials, dedoping process 100 ~ 300s is carried out to the working electrode after polyreaction, the working electrode after dedoping is cleaned with electroanalysis solvent B, put into 50 ~ 80 DEG C of vacuum drying chambers afterwards and dry 5 ~ 10h, obtain described negative material;
In step (3), described three-electrode cell take conductive substrates as working electrode, and described conductive substrates is selected from ito glass electrode, ITO-PET flexible electrode; With gold or platinum electrode for auxiliary electrode; With mercurous chloride electrode or silver-silver chloride electrode for contrast electrode;
Described electroanalysis solvent B is acetonitrile, methylene chloride, acetonitrile-dichloromethane mixed liquor or deionized water;
Described monomers B is EDOT, and described monomers B initial concentration is in the electrolytic solution 0.002 ~ 0.1mol/L;
Described supporting electrolyte B is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, and described supporting electrolyte B concentration is in the electrolytic solution 0.01 ~ 1mol/L;
(4) assembling of monolayer solid device: the solid electrolyte that step (1) is obtained is laid on the obtained positive electrode of step (2), then the negative material that step (3) is obtained is covered above solid electrolyte, obtain the material with three-layer sandwich structure, be placed in 40 ~ 70 DEG C of baking ovens and heat 3 ~ 7h, obtain the described solid electrolyte electrochromism flexible device based on conducting polymer.
2. preparation method as claimed in claim 1, is characterized in that, in step (1), described polymeric plasticizer is for being polymethylmethacrylate.
3. preparation method as claimed in claim 1, it is characterized in that, in step (1), described macromolecule sweller is carbonic allyl ester.
4. preparation method as claimed in claim 1, it is characterized in that, in step (1), described supporting electrolyte X is LiBF4.
5. preparation method as claimed in claim 1, it is characterized in that, in step (1), described doping electrolyte is 1-butyl-3-methylimidazole fluoroform sulphonate.
6. preparation method as claimed in claim 1, it is characterized in that, in step (2), described supporting electrolyte A is sulfuric acid.
7. preparation method as claimed in claim 1, it is characterized in that, in step (3), described supporting electrolyte B is tetrabutylammonium perchlorate.
8. preparation method as claimed in claim 1, is characterized in that, step (4), in an oven in heating process, is used hand extrusion device every half an hour, positive and negative electrode material and solid electrolyte are enough bonded.
9. the preparation method based on the solid electrolyte electrochromism flexible device of conducting polymer, it is characterized in that, the preparation of preparation method's step (2) positive electrode according to claim 1 replaced with and be prepared by following spin-coating method, all the other are identical:
By polymer electrochromic material dissolves in a solvent, obtain the solution of polymer electrochromic material, drip above-mentioned solution on a flexible substrate, make it to cover flexible substrates completely, leave standstill 2 ~ 15min, then open spin coating instrument and be divided into three phases and carry out spin coating:
First stage: be 300 ~ 700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution;
Subordinate phase: first grade: be 300 ~ 700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution; Second gear: be 1300 ~ 1700 revs/min by spin coating instrument rotational speed regulation, set of time is 2 ~ 4min, turns while drip solution equally;
Phase III: repeat the process of subordinate phase, finally drying at room temperature under nitrogen protection, obtain described positive electrode;
Described polymer electrochromic material is polyaniline;
Described solvent is 1-Methyl-2-Pyrrolidone;
In the solution of described polymer electrochromic material, the concentration of polymer electrochromic material is 0.01 ~ 0.03g/mL;
Described flexible substrates is ITO-PET.
10. preparation method as claimed in claim 9, it is characterized in that, in the described first stage, spin coating instrument rotating speed is 500 revs/min, and the time is 3min; In second and third stage, first grade of spin coating instrument rotating speed is 500 revs/min, and the time is 3min, and second gear spin coating instrument rotating speed is 1500 revs/min, and the time is 3min.
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