CN105372896B - Preparation method of solid electrolyte electrochromic flexible device based on conductive polymer - Google Patents
Preparation method of solid electrolyte electrochromic flexible device based on conductive polymer Download PDFInfo
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- CN105372896B CN105372896B CN201510810819.9A CN201510810819A CN105372896B CN 105372896 B CN105372896 B CN 105372896B CN 201510810819 A CN201510810819 A CN 201510810819A CN 105372896 B CN105372896 B CN 105372896B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000007787 solid Substances 0.000 claims abstract description 34
- 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
- 239000003792 electrolyte Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 39
- 239000003115 supporting electrolyte Substances 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 238000004528 spin coating Methods 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 239000011521 glass Substances 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000002322 conducting polymer Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 229920002521 macromolecule Polymers 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 230000005611 electricity Effects 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000002604 ultrasonography Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- -1 4-butyl ammonium fluoroborate Chemical group 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 11
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical group [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 claims description 11
- 230000033228 biological regulation Effects 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 10
- 230000008961 swelling Effects 0.000 claims description 10
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000008151 electrolyte solution Substances 0.000 claims description 8
- 229920000767 polyaniline Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- RAFKCLFWELPONH-UHFFFAOYSA-N acetonitrile;dichloromethane Chemical group CC#N.ClCCl RAFKCLFWELPONH-UHFFFAOYSA-N 0.000 claims description 6
- 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 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
- 229910001496 lithium tetrafluoroborate Chemical group 0.000 claims description 6
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 5
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229940075397 calomel Drugs 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical group CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical group O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 15
- 238000012545 processing Methods 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 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 2
- 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229920006254 polymer film Polymers 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 238000012549 training Methods 0.000 description 4
- 239000012780 transparent material Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000004984 smart glass Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 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
- LMMSDELZDNNQAN-UHFFFAOYSA-N C=C(F)F.C(=C(Cl)Cl)(C(Cl)(Cl)Cl)Cl Chemical group C=C(F)F.C(=C(Cl)Cl)(C(Cl)(Cl)Cl)Cl LMMSDELZDNNQAN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000139306 Platt Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RTZKMGZSJBRJFI-UHFFFAOYSA-N boric acid;lithium Chemical compound [Li].OB(O)O RTZKMGZSJBRJFI-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 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
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000005538 encapsulation 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 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
- 229920000131 polyvinylidene 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
- 238000011160 research Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
-
- 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 methods of electrochromic device, and in particular to a kind of solid based on conducting polymer
The preparation method of electrolyte electrochromism flexible device.
(2) background technology
Electrochromism phenomenon refers under DC Electric Field, due to redox reaction or charge (electronics or ion)
Injection or extraction process, the optical property (including transmissivity, absorptivity and reflectivity etc.) of material is in visible wavelength model
Interior generation inverible transform is enclosed, macro manifestations are that the color of material has reversible transformation with DC Electric Field.From twentieth century
Since sixties Platt propose electrochromism concept, electrochromic material causes people's extensive concern.According to the knot of material
Structure is different, can be divided into inorganic electrochromic material and organic electrochromic material.The research work of early stage is concentrated mainly on nothing
Machine electrochromic material, including transition metal oxide, such as tungstic acid (WO3), iridium dioxide (IrO2), Prussian blue system
Deng.Inorganic electrochromic material has good photochemical stability, but its processability, color plasticity is not strong, coloration efficiency
It is not high, limit its large-scale application in production and living.And organic molecule and conducting polymer base electrochromic material
(including viologen organic micromolecule, polypyrrole, polythiophene, polyaniline, polybenzazole, poly- furans and corresponding derivative etc. are led
Electric polymer) deficiency that inorganic electrochromic material can be made up, gradually it is valued by people.Wherein conducting polymer is electroluminescent
Off-color material has that structure species are more, color change interval is wide, optical contrast is high, processing performance is good and fast response time etc. is excellent
Point, it is considered to be one of the developing direction of next-generation electrochromism (EC) material is prepared high performance electroluminescent for further exploitation
Discoloration solid state device provides good material foundation.
In Material Field, currently there are electrochromic device anode mostly use inorganic electrochromic material, this
Conversion between the usually only single coloured state of material and transparent state or two kinds of colors a bit, transition response is slow, usually wants
Reach tens seconds, and optical contrast is not high, therefore is difficult the requirement for meeting high-end electrochromic device.Organic molecule EC
Material color is abundant, and the response time is also than very fast, but stability is very poor, it is difficult to ensure the long-time service of device.And polymer
The display of a variety of different colours may be implemented by means such as the structure design of monomer and copolymerization for electrochromic material, response
Speed is much better than traditional inorganic electrochromic material, and stability has larger improvement than organic molecule.
And in terms of device electrolyte, current main electrolyte is the electrolysis of liquid electrolyte or dense fluids shape
Matter, for this kind of electrolyte although conductivity is pretty good, electrochemical stability is poor, requires encapsulation condition high, it is easy to leakage, one
Denier leakage and for a long time place environmental stability it is also very poor, cause service life low, the solid electrolyte studied at present is generally saturating
Bright property is all very poor, thus find a kind of high conductivity and transmissivity it is high solid electrolyte it is extremely urgent.
Currently, in the market the display devices such as existing display, Electronic Paper, electric advertisement screen mostly using liquid crystal or
Person's electrophoretic techniques.Liquid crystal energy consumption is big, opaque and cannot achieve Flexible Displays；Electrophoresis be typically only capable to show it is transparent with it is opaque
Or fixed several colors.The present invention prepare based on conducting polymer electrochromic material monolayer solid device, no matter in work(
Energy material selection, the stabilization of device, color, energy consumption etc. embody apparent advantage, are high-performance conductive electrostrictive polymer
Mutagens color material solid device lays good basis in display device, smart window, the technical fields such as automobile rearview mirror.
However, conducting polymer electrochromic material is not also big in fields such as display technology, smart window, auto industrys at present
Area commercial application, or even the country there is no the producer of PEC materials and its solid state device large-scale production at present.Main cause has
The following：The first, the technology of preparing of the PEC materials of high-performance and low-cost is not mature enough, and basic theory is also incomplete；The
Two, the design and assembling of the PEC material solid devices with excellent properties are also in design development phase, and main there are three aspects
Problem：(1) high performance solid electrolyte, (2) high performance electrode material, the rational design and assembling of (3) solid state device
Technology.The present invention is mainly explored in terms of the package technique of the innovative preparation of solid electrolyte material and device,
And the conducting polymer electrochromic material solid state device with polychrome, quick response is successfully prepared.
(3) invention content
The technical problem to be solved in the present invention is to provide a kind of simple for process, of low cost, performance stabilization based on conduction
The preparation method of the solid electrolyte electrochromism flexible device of polymer, mainly solving the technical problems that solid electrolyte
Preparation and the assembling of solid state device.
A kind of preparation method of solid electrolyte electrochromism flexible device based on conducting polymer of the present invention
Include mainly：The preparation of positive and negative electrode electrode material, the preparation of solid electrolyte, the design of device architecture, device assembling.
The present invention adopts the following technical scheme that：
A kind of preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer, the preparation side
Method includes the following steps：
(1) preparation of solid electrolyte：Polymeric plasticizer and macromolecule sweller are mixed, 50~80 DEG C of baking is placed in
In case heating swelling 10~for 24 hours, be denoted as system A；Supporting electrolyte X, doping electrolyte and electroanalysis solvent X are mixed, in 50~
100KHz 2~10h of ultrasound, are denoted as system B；The system A is mixed with system B, and by gained mixture in 50~100KHz
2~10h of ultrasound, be placed in 70~90 DEG C of vacuum drying chambers 5~15h of standing, obtain the solid electrolyte；
In step (1), the polymeric plasticizer is polymethyl methacrylate (PMMA), polyvinylidene fluoride
(PVDF) or it is poly- (vinylidene fluoride-hexachloropropylene) (PVDF-HFP), preferably polymethyl methacrylate (PMMA)；
The macromolecule sweller is propene carbonate (PC) or polyethylene glycol, preferably propene carbonate (PC)；
The supporting electrolyte X is tetrabutylammonium perchlorate, lithium perchlorate, 4-butyl ammonium fluoroborate or tetrafluoro boric acid
Lithium, preferably LiBF4；
The doping electrolyte is 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- butyl -3- methylimidazole hexafluoro phosphorus
Hydrochlorate, 1- butyl -3- methylimidazoles fluoroform sulphonate or bis- (trifluoro methylsulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles, it is excellent
It is selected as 1- butyl -3- methylimidazole fluoroform sulphonates；
The electroanalysis solvent X is acetonitrile, dichloromethane, isopropanol or acetonitrile-dichloromethane mixed solvent, preferably second
Nitrile-methylene chloride volume is than 3：7 mixed solvent；
In the system A, the mass ratio of polymeric plasticizer and macromolecule sweller is 1：1.5~4；In the system B,
The mass ratio of supporting electrolyte X, doping electrolyte and electroanalysis solvent X are 1：2~5：5~30；The matter of the system A and system B
Amount is than being 1：0.22~1.97.
(2) preparation of positive electrode：Electroanalysis solvent A, monomer A and supporting electrolyte A are hybridly prepared into electrolyte to be added
In three-electrode cell, polymerisation is carried out using potentiostatic method under the conditions of 0.7~1.52V, when polymerization consumption electricity reaches
Polymerization terminates when 0.01~0.15C, is -0.2~-1.2V by control of Electric potentials, and de- mix is carried out to the working electrode after polymerisation
100~300s of reason is lived together, the working electrode after cleaning dedoping with electrolysis solvent A is put into 50~80 DEG C of vacuum drying chambers later
5~10h of middle drying obtains the positive electrode；
In step (2), the three-electrode cell is using conductive substrates as working electrode, preferably ITO (tin indium oxide)
Glass electrode, ITO-PET (pet material for being coated with conductive indium-tin oxide layer) flexible electrode；With gold or
Platinum electrode is auxiliary electrode, preferably platinum electrode；Using calomel electrode or silver-silver chloride electrode as reference electrode, preferably silver-chlorine
Change silver electrode；
The electroanalysis solvent A is acetonitrile, dichloromethane, acetonitrile-dichloromethane mixed liquor or deionized water, is preferably gone
Ionized water；
The monomer A is thiophene-based, triphen amine or carbazole organic micromolecule, specially aniline or TBTPA (three
Aniline coupling thiophene), the initial concentrations of the monomer A in the electrolytic solution are 0.01~0.6mol/L；
The supporting electrolyte A be tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, preferably
For sulfuric acid, a concentration of 0.01~5mol/L of the supporting electrolyte A in the electrolytic solution；
The positive electrode of gained is to deposit the conductive substrates for having thin polymer film；
(3) preparation of negative material：Electroanalysis solvent B, monomer B and supporting electrolyte B are hybridly prepared into electrolyte to be added
In three-electrode cell, polymerisation is carried out using potentiostatic method under the conditions of 0.7~1.52V, when polymerization consumption electricity reaches
Polymerization terminates when 0.01~0.15C, is -0.2~-0.6V by control of Electric potentials, and de- mix is carried out to the working electrode after polymerisation
100~300s of reason is lived together, the working electrode after cleaning dedoping with electroanalysis solvent B is put into 50~80 DEG C of vacuum drying chambers later
5~10h of middle drying obtains the negative material；
In step (3), the three-electrode cell is using conductive substrates as working electrode, preferably ITO (tin indium oxide)
Glass electrode, ITO-PET (pet material for being coated with conductive indium-tin oxide layer) flexible electrode；With gold or
Platinum electrode is auxiliary electrode, preferably platinum electrode；Using calomel electrode or silver-silver chloride electrode as reference electrode, preferably silver-chlorine
Change silver electrode；
The electroanalysis solvent B is acetonitrile, dichloromethane, acetonitrile-dichloromethane mixed liquor or deionized water, preferably second
Nitrile-methylene chloride volume is than 1：2~5 mixed liquor；
The monomer B is thiophene-based, triphen amine, carbazole organic micromolecule, specially EDOT (3,4- ethylene dioxies
Thiophene), the initial concentrations of the monomer B in the electrolytic solution are 0.002~0.1mol/L；
The supporting electrolyte B be tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, preferably
For tetrabutylammonium perchlorate, a concentration of 0.01~1mol/L of the supporting electrolyte B in the electrolytic solution；
The negative material of gained is to deposit the conductive substrates for having thin polymer film；
(4) assembling of monolayer solid device：It is obtained just that solid electrolyte made from step (1) is laid in step (2)
On the material of pole, then negative material made from step (3) is covered in above solid electrolyte, is obtained with three-layer sandwich structure
Material, place it in 40~70 DEG C of baking ovens heat 3~7h (in the heating process, hand squeezer can be used every half an hour
Part makes positive and negative electrode material be bonded enough with solid electrolyte) it is electroluminescent to get the solid electrolyte based on conducting polymer
Color-changing flexible device.
In the present invention, the positive electrode can also be prepared by following spin-coating method：
In a solvent by the dissolving of polymer electrochromic material, the solution of polymer electrochromic material is obtained, in flexibility
Above-mentioned solution is added dropwise in substrate, is allowed to that flexible substrates are completely covered, stands 2~15min, be then turned on spin coating instrument and be divided into three ranks
Duan Jinhang spin coatings：
First stage：It it is 300~700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, is added dropwise when turning
Solution；
Second stage：First grade：It it is 300~700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, side
Turn side and solution is added dropwise；Second gear：It it is 1300~1700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, equally
Solution is added dropwise when turning；
Phase III：Repeat second stage process, finally under nitrogen protection drying at room temperature to get the positive material
Material；
The polymer electrochromic material is polyaniline；
The solvent is 1-Methyl-2-Pyrrolidone；
A concentration of 0.01~0.03g/ of polymer electrochromic material in the solution of the polymer electrochromic material
mL；
The flexible substrates are ITO-PET (pet material for being coated with conductive indium-tin oxide layer).
During the spin-coating method prepares positive electrode, preferably first stage spin coating instrument rotating speed is 500 revs/min, the time
For 3min；
In second and third stage, preferably first grade of spin coating instrument rotating speed is 500 revs/min, time 3min；It is preferred that second gear revolves
It is 1500 revs/min to apply instrument rotating speed, time 3min.
In the present invention, term " system A ", " system B " not special meaning is only intended to distinguish labeled as " A ", " B "
Different systems.Term " supporting electrolyte X ", " supporting electrolyte A ", " supporting electrolyte B " also not special meaning, label
It is only intended to distinguish the supporting electrolyte used in different step for " X ", " A ", " B ", " electroanalysis solvent X ", " electroanalysis solvent A ",
" electroanalysis solvent B ", " monomer A ", " monomer B " are therewith similarly.
The present invention characterizes obtained solid device by cyclic voltammetry, it was confirmed that solid state device has electroluminescent change
Different color changes can be achieved in color performance that is, in certain voltage range；It is tested by more potential step methods, it was confirmed that single
Layer solid state device has the performance of quick color change, and has carried out the test of response speed to device, it was demonstrated that it responds speed
Degree is a kind of device that electrochromic property is excellent quickly.
Compared with prior art, the beneficial effects are mainly as follows：
(1) solid electrolyte used in the present invention is prepared for laboratory autonomous Design, and preparation method is easy, ambient stable
Property it is good, and do not need harsh reaction condition, can be carried out operating at room temperature；
(2) the conducting polymer electrochromic material that the present invention uses has structure compared with inorganic and organic molecule
The advantages that type is more, color change interval is wide, optical contrast is high, processing performance is good and fast response time；
(3) conducting polymer base solid state device film of the present invention has electrochromic performance, thus in display, intelligence
The fields such as window, Electronic Paper have huge application prospect；
(4) electrochromic material of the present invention has many advantages, such as that driving voltage is low, memory for color effect so that its power saving effect
It is prominent, and passive shine is more advantageous to the protection of human eye.
(4) it illustrates
Fig. 1 a, 1b are the flexible solid device that is assembled in embodiment 1 in energization (0.9V, Fig. 1 a) and are not powered on down (0V, figure
Diagram 1b)；
Fig. 2 a, 2b are the flexible solid device that is assembled in embodiment 2 in energization (0.9V, Fig. 2 a) and are not powered on (0V, figure
Diagram under 2b)；
Fig. 3 a, 3b are the flexible solid device that is assembled in embodiment 3 in energization (0.9V, Fig. 3 a) and are not powered on (0V, figure
Diagram under 3b)；
Fig. 4 a, 4b are the flexible solid device that is assembled in embodiment 4 in energization (0.9V, Fig. 4 a) and are not powered on (0V, figure
Diagram under 4b).
(5) specific implementation mode
Technical scheme of the present invention is further described with specific embodiment below, but protection scope of the present invention is not
It is limited to this.
Embodiment 1
A kind of preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer, including following step
Suddenly：
(1) solid electrolyte is prepared：It is empty that band is added in polymeric plasticizer PMMA 1.75g and macromolecule sweller PC 5g
In the round-bottomed flask of heart plug or reagent bottle with a lid, it is placed in heating swelling 12h in 70 DEG C of baking oven, makes macromolecule transparent material
Good swelling is denoted as system A in macromolecule sweller.By supporting electrolyte LiBF40.24g and doping electrolyte 1- fourths
Round-bottomed flask is added in base -3- methylimidazole fluoroform sulphonate 0.8g and electroanalysis solvent (acetonitrile 3g- dichloromethane 0.75g)
In, opening is placed in ultrasound 5h in 80KHz ultrasounds pond, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent,
It is denoted as system B.System A, system B are poured in the same round-bottomed flask with hollow plug or reagent bottle with a lid and mixed, it
Mixture makes mixture that gel be presented, pours into culture dish later in 80KHz ultrasound 7h afterwards, and by the training equipped with mixture
Foster ware is put into vacuum drying chamber (82 DEG C), places 10h, and finally obtained electrolyte is in flexible solid shape, somewhat viscous, thickness
For 0.8mm.
(2) positive electrode is prepared：Monomer A is aniline, and structure is as follows：
Monomer aniline 2.328g and 98% sulfuric acid 5g are uniformly hybridly prepared into electrolyte in 50ml volumetric flasks, and (solvent is
Deionized water), then electrolyte is added in three-electrode cell, wherein working electrode is ITO conductive glass electrodes (its ruler
Very little is 2cm × 2cm), auxiliary electrode is platinum electrode, and reference electrode is silver-silver chloride electrode.It is adopted under the conditions of polymerizeing current potential 0.7V
Polymerisation is carried out with potentiostatic method, when polymerization consumption electricity reaches 0.06C, polymerization terminates, working electrode ITO electro-conductive glass tables
Face deposited the polymer film of blue layer, be -0.2V by control of Electric potentials, and dedoping is carried out to the working electrode after polymerisation
100s is handled, the working electrode after then cleaning dedoping with deionized water is put into 70 DEG C of vacuum drying chambers and dries 7h, obtains
Positive electrode (deposition has the ITO conductive glass electrodes of conducting polymer thin film) is for use.
(3) negative material is prepared：Monomer B is EDOT, and monomer 0.355g and tetrabutylammonium perchlorate 1.71g is held in 50ml
It is uniformly hybridly prepared into electrolyte (solvent is acetonitrile) in measuring bottle, then electrolyte is added in three-electrode cell, wherein
Working electrode is ITO conductive glass electrodes (its size is 2cm × 2cm), and auxiliary electrode is platinum electrode, and reference electrode is silver-chlorine
Change silver electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerizeing current potential 1.4V, polymerization consumption electricity reaches 0.04C
When, polymerization terminates, and working electrode ITO conductive glass surfaces deposited the polymer film of blue layer, is -0.6V by control of Electric potentials
When, to the working electrode progress dedoping processing 100s after polymerisation, the working electrode after then cleaning dedoping with acetonitrile,
It is put into 70 DEG C of vacuum drying chambers and dries 7h, obtaining negative material, (deposition has the ITO electro-conductive glass electricity of conducting polymer thin film
Pole) it is for use.
(4) assembly device：Solid electrolyte made from step (1) is cut into effective with positive electrode made from step (2)
The identical square of size, is laid on positive electrode, later covers negative material made from step (3) in solid electrolytic
It above matter, is gently pressed with hand, puts heating 6h (temperature 60 C) in an oven, every half an hour hand extrusion device, ensure positive and negative electrode
Material bonds enough with solid electrolyte, obtains the device.
(5) performance test：The solid state device of gained in step (4) is tested with electrochemical workstation, is lied prostrate in cycle
The reversible change that blackish green-green color-blue has occurred in device color can be observed in peace scanning process.Fig. 1 a, 1b are step (4)
In device obtained under energized state (0.9V, Fig. 1 a) and the color that is not powered under (0V, Fig. 1 b) state.
Embodiment 2
(1) solid electrolyte is prepared：It is empty that band is added in polymeric plasticizer PMMA 1.75g and macromolecule sweller PC 3g
In the round-bottomed flask of heart plug or reagent bottle with a lid, it is placed in heating swelling 12h in 70 DEG C of baking oven, makes macromolecule transparent material
Good swelling is denoted as system A in macromolecule sweller.By supporting electrolyte LiBF40.14g and doping electrolyte 1- fourths
Round-bottomed flask is added in base -3- methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g- dichloromethane 0.75g)
In, opening is placed in ultrasound 5h in 80KHz ultrasounds pond, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent,
It is denoted as system B.System A, system B are poured in the same round-bottomed flask with hollow plug or reagent bottle with a lid and mixed, it
Mixture makes mixture that gel be presented, pours into culture dish later in 80KHz ultrasound 7h afterwards, and by the training equipped with mixture
Foster ware is put into vacuum drying chamber (82 DEG C), places 10h, and finally obtained electrolyte is in flexible solid shape, somewhat viscous, thickness
For 0.8mm.
(2) positive electrode is prepared：Monomer A is aniline, and monomer aniline 2.328g and 98% sulfuric acid 5g are in 50ml volumetric flasks
It uniformly is hybridly prepared into electrolyte (solvent is deionized water), then electrolyte is added in three-electrode cell, wherein work
It is ITO conductive glass electrodes (its size is 2cm × 2cm) to make electrode, and auxiliary electrode is platinum electrode, and reference electrode is silver-chlorination
Silver electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerizeing current potential 0.7V, when polymerization consumption electricity reaches 0.06C,
Polymerization terminates, and working electrode ITO conductive glass surfaces deposited the polymer film of blue layer, is -0.2V by control of Electric potentials, right
Working electrode progress dedoping processing 100s after polymerisation, the working electrode after then cleaning dedoping with deionized water,
It is put into 70 DEG C of vacuum drying chambers and dries 7h, obtaining positive electrode, (deposition has the ITO electro-conductive glass electricity of conducting polymer thin film
Pole) it is for use.
(3) negative material is prepared：Monomer B is EDOT, and monomer 0.355g and tetrabutylammonium perchlorate 1.71g is held in 50ml
It is uniformly hybridly prepared into electrolyte (solvent is acetonitrile) in measuring bottle, then electrolyte is added in three-electrode cell, wherein
Working electrode is ITO conductive glass electrodes (its size is 2cm × 2cm), and auxiliary electrode is platinum electrode, and reference electrode is silver-chlorine
Change silver electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerizeing current potential 1.4V, polymerization consumption electricity reaches 0.04C
When, polymerization terminates, and working electrode ITO conductive glass surfaces deposited the polymer film of blue layer, is -0.6V by control of Electric potentials
When, to the working electrode progress dedoping processing 100s after polymerisation, the working electrode after then cleaning dedoping with acetonitrile,
It is put into 70 DEG C of vacuum drying chambers and dries 7h, obtaining negative material, (deposition has the ITO electro-conductive glass electricity of conducting polymer thin film
Pole) it is for use.
(4) assembly device：Solid electrolyte made from step (1) is cut into effective with positive electrode made from step (2)
The identical square of size, is laid on positive electrode, later covers negative material made from step (3) in solid electrolytic
It above matter, is gently pressed with hand, puts heating 6h (temperature 60 C) in an oven, every half an hour hand extrusion device, ensure positive and negative electrode
Material bonds enough with solid electrolyte, obtains the device.
(5) performance test：The solid state device of gained in step (4) is tested with electrochemical workstation, is lied prostrate in cycle
The reversible change that blackish green-green color-blue has occurred in device color can be observed in peace scanning process.Fig. 2 a, 2b are step (4)
In device obtained under energized state (0.9V, Fig. 2 a) and the color that is not powered under (0V, Fig. 2 b) state.
Embodiment 3
(1) solid electrolyte is prepared：It is empty that band is added in polymeric plasticizer PMMA 1.75g and macromolecule sweller PC 3g
In the round-bottomed flask of heart plug or reagent bottle with a lid, it is placed in heating swelling 12h in 70 DEG C of baking oven, makes macromolecule transparent material
Good swelling is denoted as system A in macromolecule sweller.By supporting electrolyte LiBF40.14g and doping electrolyte 1- fourths
Round-bottomed flask is added in base -3- methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g- dichloromethane 0.75g)
In, opening is placed in ultrasound 5h in 80KHz ultrasounds pond, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent,
It is denoted as system B.System A, system B are poured in the same round-bottomed flask with hollow plug or reagent bottle with a lid and mixed, it
Mixture makes mixture that gel be presented, pours into culture dish later in 80KHz ultrasound 7h afterwards, and by the training equipped with mixture
Foster ware is put into vacuum drying chamber (82 DEG C), places 10h, and finally obtained electrolyte is in flexible solid shape, somewhat viscous, thickness
For 0.88mm.
(2) positive electrode (spin-coating method) is prepared：Polyaniline 5g is dissolved in 250mL N-methyl pyrrolidones, is gathered
Aniline solution is poured into conical flask, is carried out spin coating by spin coating instrument later, is added dropwise 3 on flexible substrates ITO-PET first
Above-mentioned polyaniline solutions are dripped, are allowed to cover flexible substrates completely, 2 minutes is stood, starts the spin coating of spin coating instrument later three times：1. will turn
Speed is adjusted to 700 revs/min, and the time is set as 2min, and solution is added dropwise when turning, 2. first grade：It is 700 revs/min by rotational speed regulation,
Time is set as 2min, second gear：It it is 1500 revs/min by rotational speed regulation, the time is set as 2min.It is equally added dropwise when turning molten
Liquid.3. repeating 2. step, finally dried at room temperature to get positive electrode in nitrogen protection.
(3) negative material is prepared：Monomer B is EDOT, and monomer 0.355g and tetrabutylammonium perchlorate 1.71g is held in 50ml
It is uniformly hybridly prepared into electrolyte (solvent is acetonitrile) in measuring bottle, then electrolyte is added in three-electrode cell, wherein
Working electrode is ITO conductive glass electrodes (its size is 2cm × 2cm), and auxiliary electrode is platinum electrode, and reference electrode is silver-chlorine
Change silver electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerizeing current potential 1.4V, polymerization consumption electricity reaches 0.04C
When, polymerization terminates, and working electrode ITO conductive glass surfaces deposited the polymer film of blue layer, is -0.6V by control of Electric potentials
When, to the working electrode progress dedoping processing 100s after polymerisation, the working electrode after then cleaning dedoping with acetonitrile,
It is put into 70 DEG C of vacuum drying chambers and dries 7h, obtaining negative material, (deposition has the ITO electro-conductive glass electricity of conducting polymer thin film
Pole) it is for use.
(4) assembly device：Solid electrolyte made from step (1) is cut into effective with positive electrode made from step (2)
The identical square of size, is laid on positive electrode, later covers negative material made from step (3) in solid electrolytic
It above matter, is gently pressed with hand, puts heating 6h (temperature 60 C) in an oven, every half an hour hand extrusion device, ensure positive and negative electrode
Material bonds enough with solid electrolyte, obtains the device.
(5) performance test：The solid state device of gained in step (4) is tested with electrochemical workstation, is lied prostrate in cycle
The reversible change that blackish green-green color-blue has occurred in device color can be observed in peace scanning process.Fig. 3 a, 3b are step (4)
In device obtained under energized state (0.9V, Fig. 3 a) and the color that is not powered under (0V, Fig. 3 b) state.
Embodiment 4
(1) solid electrolyte is prepared：It is empty that band is added in polymeric plasticizer PMMA 1.75g and macromolecule sweller PC 3g
In the round-bottomed flask of heart plug or reagent bottle with a lid, it is placed in heating swelling 12h in 70 DEG C of baking oven, makes macromolecule transparent material
Good swelling is denoted as system A in macromolecule sweller.By supporting electrolyte LiBF40.14g and doping electrolyte 1- fourths
Round-bottomed flask is added in base -3- methylimidazole fluoroform sulphonate 0.5g and electroanalysis solvent (acetonitrile 3g- dichloromethane 0.75g)
In, opening is placed in ultrasound 5h in 80KHz ultrasounds pond, until supporting electrolyte, doping electrolyte are dissolved completely in electroanalysis solvent,
It is denoted as system B.System A, system B are poured in the same round-bottomed flask with hollow plug or reagent bottle with a lid and mixed, it
Mixture makes mixture that gel be presented, pours into culture dish later in 80KHz ultrasound 7h afterwards, and by the training equipped with mixture
Foster ware is put into vacuum drying chamber (82 DEG C), places 10h, and finally obtained electrolyte is in flexible solid shape, somewhat viscous, thickness
For 0.88mm.
(2) positive electrode (spin-coating method) is prepared：Polyaniline 5g is dissolved in 250mL N-methyl pyrrolidones, is gathered
Aniline solution is poured into conical flask, is carried out spin coating by spin coating instrument later, is added dropwise 3 on flexible substrates ITO-PET first
Above-mentioned polyaniline solutions are dripped, are allowed to cover flexible substrates completely, 5 minutes is stood, starts the spin coating of spin coating instrument later three times：1. will turn
Speed is adjusted to 500 revs/min, and the time is set as 3min, and solution is added dropwise when turning, 2. first grade：It is 500 revs/min by rotational speed regulation,
Time is set as 3min, second gear：It it is 1500 revs/min by rotational speed regulation, the time is set as 3min.It is equally added dropwise when turning molten
Liquid.3. repeating 2. step, finally dried at room temperature to get positive electrode in nitrogen protection.
(3) negative material is prepared：Monomer B is EDOT, and monomer 0.355g and tetrabutylammonium perchlorate 1.71g is held in 50ml
It is uniformly hybridly prepared into electrolyte (solvent is acetonitrile) in measuring bottle, then electrolyte is added in three-electrode cell, wherein
Working electrode is ITO conductive glass electrodes (its size is 2cm × 2cm), and auxiliary electrode is platinum electrode, and reference electrode is silver-chlorine
Change silver electrode.Polymerisation is carried out using potentiostatic method under the conditions of polymerizeing current potential 1.4V, polymerization consumption electricity reaches 0.04C
When, polymerization terminates, and working electrode ITO conductive glass surfaces deposited the polymer film of blue layer, is -0.6V by control of Electric potentials
When, to the working electrode progress dedoping processing 100s after polymerisation, the working electrode after then cleaning dedoping with acetonitrile,
It is put into 70 DEG C of vacuum drying chambers and dries 7h, obtaining negative material, (deposition has the ITO electro-conductive glass electricity of conducting polymer thin film
Pole) it is for use.
(4) assembly device：Solid electrolyte made from step (1) is cut into effective with positive electrode made from step (2)
The identical square of size, is laid on positive electrode, later covers negative material made from step (3) in solid electrolytic
It above matter, is gently pressed with hand, puts heating 6h (temperature 60 C) in an oven, every half an hour hand extrusion device, ensure positive and negative electrode
Material bonds enough with solid electrolyte, obtains the device.
(5) performance test：The solid state device of gained in step (4) is tested with electrochemical workstation, is lied prostrate in cycle
The reversible change that blackish green-green color-blue has occurred in device color can be observed in peace scanning process.Fig. 4 a, 4b are step (4)
In device obtained under energized state (0.9V, Fig. 4 a) and the color that is not powered under (0V, Fig. 4 b) state.
Claims (10)
1. a kind of preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer, which is characterized in that institute
The preparation method stated includes the following steps：
(1) preparation of solid electrolyte：Polymeric plasticizer and macromolecule sweller are mixed, are placed in 50~80 DEG C of baking oven
Heating swelling 10~for 24 hours, it is denoted as system A；Supporting electrolyte X, doping electrolyte and electroanalysis solvent X are mixed, in 50~
100KHz 2~10h of ultrasound, are denoted as system B；The system A is mixed with system B, and by gained mixture in 50~100KHz
2~10h of ultrasound, be placed in 70~90 DEG C of vacuum drying chambers 5~15h of standing, obtain the solid electrolyte；
In step (1), the polymeric plasticizer is polymethyl methacrylate, polyvinylidene fluoride or poly- (inclined difluoro second
Alkene-hexachloropropylene)；
The macromolecule sweller is propene carbonate or polyethylene glycol；
The supporting electrolyte X is tetrabutylammonium perchlorate, lithium perchlorate, 4-butyl ammonium fluoroborate or LiBF4；
The doping electrolyte is 1- butyl -3- methyl imidazolium tetrafluoroborates, 1- butyl -3- methylimidazole hexafluorophosphoric acids
Salt, 1- butyl -3- methylimidazoles fluoroform sulphonate or bis- (trifluoro methylsulfonyl) inferior amine salts of 1- butyl -3- methylimidazoles；
The electroanalysis solvent X is acetonitrile, dichloromethane, isopropanol or acetonitrile-dichloromethane mixed solvent；
In the system A, the mass ratio of polymeric plasticizer and macromolecule sweller is 1：1.5~4；In the system B, support
The mass ratio of electrolyte X, doping electrolyte and electroanalysis solvent X are 1：2~5：5~30；The mass ratio of the system A and system B
It is 1：0.22~1.97；
(2) preparation of positive electrode：Electroanalysis solvent A, monomer A and supporting electrolyte A are hybridly prepared into electrolyte, three electricity are added
In the electrolytic cell of pole, polymerisation is carried out using potentiostatic method under the conditions of 0.7~1.52V, when polymerization consumption electricity reaches 0.01
Polymerization terminates when~0.15C, is -0.2~-1.2V by control of Electric potentials, is carried out at dedoping to the working electrode after polymerisation
100~300s is managed, the working electrode after cleaning dedoping with electrolysis solvent A is put into 50~80 DEG C of vacuum drying chambers and dries later
Dry 5~10h, obtains the positive electrode；
In step (2), for the three-electrode cell using conductive substrates as working electrode, the conductive substrates are selected from ITO glass
Glass electrode, ITO-PET flexible electrodes；Using gold or platinum electrode as auxiliary electrode；Using calomel electrode or silver-silver chloride electrode as reference
Electrode；
The electroanalysis solvent A is acetonitrile, dichloromethane, acetonitrile-dichloromethane mixed liquor or deionized water；
The monomer A is aniline or TBTPA, and the initial concentrations of the monomer A in the electrolytic solution are 0.01~0.6mol/L；
The supporting electrolyte A is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, the support
A concentration of 0.01~the 5mol/L of electrolyte A in the electrolytic solution；
(3) preparation of negative material：Electroanalysis solvent B, monomer B and supporting electrolyte B are hybridly prepared into electrolyte, three electricity are added
In the electrolytic cell of pole, polymerisation is carried out using potentiostatic method under the conditions of 0.7~1.52V, when polymerization consumption electricity reaches 0.01
Polymerization terminates when~0.15C, is -0.2~-0.6V by control of Electric potentials, is carried out at dedoping to the working electrode after polymerisation
100~300s is managed, the working electrode after cleaning dedoping with electroanalysis solvent B is put into 50~80 DEG C of vacuum drying chambers and dries later
Dry 5~10h, obtains the negative material；
In step (3), for the three-electrode cell using conductive substrates as working electrode, the conductive substrates are selected from ITO glass
Glass electrode, ITO-PET flexible electrodes；Using gold or platinum electrode as auxiliary electrode；Using calomel electrode or silver-silver chloride electrode as reference
Electrode；
The electroanalysis solvent B is acetonitrile, dichloromethane, acetonitrile-dichloromethane mixed liquor or deionized water；
The monomer B is EDOT, and the initial concentrations of the monomer B in the electrolytic solution are 0.002~0.1mol/L；
The supporting electrolyte B is tetrabutylammonium perchlorate, lithium perchlorate, sulfuric acid or 4-butyl ammonium fluoroborate, the support
A concentration of 0.01~the 1mol/L of electrolyte B in the electrolytic solution；
(4) assembling of monolayer solid device：Solid electrolyte made from step (1) is laid in positive material made from step (2)
On material, then negative material made from step (3) is covered in above solid electrolyte, obtains the material with three-layer sandwich structure
Material places it in 40~70 DEG C of baking ovens and heats 3~7h to get the solid electrolyte electrochromism based on conducting polymer
Flexible device.
2. preparation method as described in claim 1, which is characterized in that in step (1), the polymeric plasticizer is poly-
Methyl methacrylate.
3. preparation method as described in claim 1, which is characterized in that in step (1), the macromolecule sweller is carbonic acid
Acrylic ester.
4. preparation method as described in claim 1, which is characterized in that in step (1), the supporting electrolyte X is tetrafluoro
Lithium borate.
5. preparation method as described in claim 1, which is characterized in that in step (1), the doping electrolyte is 1- fourths
Base -3- methylimidazole fluoroform sulphonates.
6. preparation method as described in claim 1, which is characterized in that in step (2), the supporting electrolyte A is sulfuric acid.
7. preparation method as described in claim 1, which is characterized in that in step (3), the supporting electrolyte B is four fourths
Base ammonium perchlorate.
8. preparation method as described in claim 1, which is characterized in that step (4) is small every half in an oven in heating process
When with hand extrusion device, so that positive and negative electrode material is bonded enough with solid electrolyte.
9. a kind of preparation method of the solid electrolyte electrochromism flexible device based on conducting polymer, which is characterized in that will
The preparation of preparation method step (2) positive electrode described in claim 1 is replaced with to be prepared by following spin-coating method, remaining
It is identical：
In a solvent by the dissolving of polymer electrochromic material, the solution of polymer electrochromic material is obtained, in flexible substrates
It is upper that above-mentioned solution is added dropwise, be allowed to that flexible substrates are completely covered, stand 2~15min, be then turned on spin coating instrument be divided into three phases into
Row spin coating：
First stage：It it is 300~700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, is added dropwise when turning molten
Liquid；
Second stage：First grade：It it is 300~700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, Bian Zhuanbian
Solution is added dropwise；Second gear：It it is 1300~1700 revs/min by spin coating instrument rotational speed regulation, the time is set as 2~4min, and same side turns
Solution is added dropwise in side；
Phase III：Repeat second stage process, finally under nitrogen protection drying at room temperature to get the positive electrode；
The polymer electrochromic material is polyaniline；
The solvent is 1-Methyl-2-Pyrrolidone；
A concentration of 0.01~0.03g/mL of polymer electrochromic material in the solution of the polymer electrochromic material；
The flexible substrates are ITO-PET.
10. preparation method as claimed in claim 9, which is characterized in that in the first stage, spin coating instrument rotating speed be 500 turns/
Point, time 3min；In second and third stage, first grade of spin coating instrument rotating speed is 500 revs/min, time 3min, second gear spin coating
Instrument rotating speed is 1500 revs/min, time 3min.
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| CN112666770B (en) * | 2021-01-12 | 2022-09-23 | 浙江工业大学 | Electrochromic flexible device based on P (SPMA-MMA) hydrogel electrolyte and preparation method and application thereof |
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