CN102759835A - Fiber-shaped flexible electrochromic device and preparation method thereof - Google Patents

Fiber-shaped flexible electrochromic device and preparation method thereof Download PDF

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CN102759835A
CN102759835A CN2012102492834A CN201210249283A CN102759835A CN 102759835 A CN102759835 A CN 102759835A CN 2012102492834 A CN2012102492834 A CN 2012102492834A CN 201210249283 A CN201210249283 A CN 201210249283A CN 102759835 A CN102759835 A CN 102759835A
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layer
gather
core
polyelectrolyte
thiophene
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CN102759835B (en
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熊善新
汪晓芹
周安宁
石玉静
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Xian University of Science and Technology
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Xian University of Science and Technology
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Abstract

The invention discloses a fiber-shaped flexible electrochromic device comprising a transparent polymer protection layer, a silver wire counter electrode, an electrochromic layer, a transparent conductive layer and a core material. The invention further discloses a preparation method of the fiber-shaped flexible electrochromic device. The method comprises the following steps of: forming the transparent conductive layer on the surface of the core material by utilizing a thermal evaporation method or an ion sputtering method; forming the electrochromic layer on the transparent conductive layer by utilizing a coating method, a solution Czochralski method or an electric deposition method; coating a gel polyelectrolyte on the surface of the electrochromic layer to form a polyelectrolyte layer; placing the silver wire counter electrode into the polyelectrolyte layer which is parallel to the core material; and then, covering a transparent polymer protection layer on the outer surface of the polyelectrolyte layer, and carrying out heat seal treatment to obtain the device. According to the fiber-shaped flexible electrochromic device and the preparation method disclosed by the invention, the process is simple and the prepared fiber-shaped flexible electrochromic device is a flexible and bendable fiber-shaped abnormal structure; and the fiber-shaped flexible electrochromic device can be used as an assembling unit of a more complicated abnormal structure device, and a method foundation for assembling the other abnormal structure devices is provided.

Description

A kind of fibrous flexible electrochromic device and preparation method thereof
Technical field
The invention belongs to the electrochromic device technical field, be specifically related to a kind of fibrous flexible electrochromic device and preparation method thereof.
Background technology
The optical characteristics of electrochromic material (color, transparency and reflectivity etc.) can realize reversible variation under extra electric field.Electrochromic device since WV low, need not that backlight, energy consumption are little, cost low and can produce characteristics such as large tracts of land and abnormally-structured device, have a wide range of applications in fields such as display device, smart window, military camouflage and anti-dazzle automobile rearview mirrors.
Existing electrochromic device is main with sandwich structure mainly, and sandwich structure is made up of two-layer transparency electrode and the electrochromic layer and the dielectric substrate that are clipped between two-layer transparency electrode.Transparency electrode mainly contains ito glass and flexible ITO/PET; Off-color material can be divided into inorganic off-color material (modal like tungstic acid, nickel oxide, molybdena and vanadium pentoxide etc.) and organic off-color material; Organic off-color material passes through the gain and loss generation oxidation-reduction reaction of electronics, thereby realizes painted and reversible variation that fade; Dielectric substrate is generally liquid, gel state and solid-state.
According to electrochromic material and electrolytical difference, the performance of various devices is also different.In general inorganic off-color material has advantages of higher stability, but variable color speed is slow and processing cost is high; The rich color of organic off-color material, variable color is fast, be easy to processing and driving voltage low, save the energy, even also keep color changeable effect after the outage, have memory function.Liquid electrolyte can give fast response speed, but device is difficult for encapsulation, is prone to take place electrolyte leakage; Solid electrolyte is then opposite; Comparatively speaking, gel electrolyte is owing to the shortcoming that combines both advantages to abandon separately is widely used.At present, electrochromic device changes very little on its configuration and structure, and abnormally-structured device then still less.
Summary of the invention
Technical matters to be solved by this invention is to be to above-mentioned deficiency of the prior art a kind of fibrous flexible electrochromic device with coaxial multi-layer filamentary structure, flexibility characteristics and unconventional different in nature structure to be provided.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of fibrous flexible electrochromic device is characterized in that; Comprise core; The outside surface of said core is provided with transparency conducting layer, and the outside surface of said transparency conducting layer is provided with electrochromic layer, and the outside surface of said electrochromic layer is provided with polyelectrolyte layer; The outside surface of said polyelectrolyte layer is provided with the transparent polymer protective seam, is placed with the filamentary silver parallel with said core in the said polyelectrolyte layer to electrode; Said polyelectrolyte layer lithium salts, polymethylmethacrylate, carbonic allyl ester and the acetonitrile that following mass percent divides of serving as reasons mixes the gel state polyelectrolyte layer of processing: lithium salts 0.5%~5%; Polymethylmethacrylate 1%~5%; Carbonic allyl ester 5%~20%; Acetonitrile 70%~85%, wherein said lithium salts are lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
Above-mentioned a kind of fibrous flexible electrochromic device is characterized in that, the thickness of said transparent polymer protective seam is 10 μ m~30 μ m, and said transparent polymer protective seam is polyethylene film or polychloroethylene film; Said filamentary silver is 0.1mm~0.2mm to the diameter of electrode.
Above-mentioned a kind of fibrous flexible electrochromic device is characterized in that the thickness of said polyelectrolyte layer is 0.25mm~0.35mm.
Above-mentioned a kind of fibrous flexible electrochromic device; It is characterized in that; The thickness of said electrochromic layer is 150nm~250nm, and the material of said electrochromic layer is for gathering (3, the 4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) or polyaniline; Or polypyrrole and derivant thereof, or polythiophene and derivant thereof; Said polypyrrole derivant is for gathering (3; 4-ethylene dioxy pyrroles), gather (3; 4-propylene dioxy pyrroles) or poly-methyl pyrrole, said polythiofuran derivative is for gathering 3 methyl thiophene, gather 3-ten alkylthrophenes, gather 3-dodecyl thiophene, gather the 3-bromo thiophene, gather 3, the 4-thioxene, gathers 2; 2 '-two thiophene or gather (3,4-propylene dioxy thiophene).
Above-mentioned a kind of fibrous flexible electrochromic device is characterized in that, said transparency conducting layer is that thickness is aluminium lamination, gold layer or the platinum layer of 20nm~40nm.
Above-mentioned a kind of fibrous flexible electrochromic device is characterized in that the diameter of said core is 0.4mm~4mm, and the material of said core is nylon, polypropylene, tygon or PVC.
The present invention also provides a kind of fibrous flexible electrochromism preparation of devices method, it is characterized in that this method comprises the steps:
Step 1, adopt surfactant and washed with de-ionized water core surface successively, the oven dry of core after will cleaning is then waited to dry back hot vapour deposition method of employing or ion sputtering method and on the core outside surface, is formed transparent metal layer as transparency conducting layer; The mass concentration of said surfactant≤5%, said surfactant are neopelex, cetyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, sodium hexadecyl sulfate, sodium dodecylsulphonate, sodium cetanesulfonate or octadecyl sodium sulfonate;
Step 2, employing cladding process, solution czochralski method or electrodeposition process form electrochromic layer on the outside surface of transparency conducting layer described in the step 1;
Step 3, lithium salts, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on the outside surface of electrochromic layer described in the step 2 and form polyelectrolyte layer;
Step 4, filamentary silver is positioned over described in the step 3 in the polyelectrolyte layer electrode, the transparent polymer protective seam is coated on the outside surface of polyelectrolyte layer described in the step 3 and through heat-seal process obtains fibrous flexible electrochromic device then.
Above-mentioned a kind of fibrous flexible electrochromism preparation of devices method is characterized in that when transparent metal layer described in the step 1 was aluminium lamination, hot vapour deposition method was adopted in the preparation of said transparent metal layer; When transparent metal layer described in the step 1 was gold layer or platinum layer, the ion sputtering method was adopted in the preparation of said transparent metal layer.
Above-mentioned a kind of fibrous flexible electrochromism preparation of devices method; It is characterized in that; Cladding process described in the step 2 is: will gather (3; The 4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) solution or polyaniline watersoluble dispersion is coated on the transparency conducting layer outside surface that has core in the step 1, said gathering (3, the 4-Ethylenedioxy Thiophene)-gather the mass concentration of (styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion is 2%~10%; The czochralski method of solution described in the step 2 is: the transparency conducting layer that has core in the step 1 is put into gathered (3, the 4-Ethylenedioxy Thiophene)-gather in (styrene sulfonic acid) solution or the polyaniline watersoluble dispersion and lift; Said gathering (3, the 4-Ethylenedioxy Thiophene)-gather, the mass concentration of (styrene sulfonic acid) solution and polyaniline watersoluble dispersion was 2%~10%.
Above-mentioned a kind of fibrous flexible electrochromism preparation of devices method; It is characterized in that electrodeposition process described in the step 2 is: with polypyrrole and derivant thereof or polythiophene and derivant thereof through electrochemical polymerization method directly on transparency conducting layer polymerization form electrochromic layer; Said polypyrrole derivant is for gathering (3; 4-ethylene dioxy pyrroles), gather (3; 4-propylene dioxy pyrroles) or poly-methyl pyrrole, said polythiofuran derivative is for gathering 3 methyl thiophene, gather 3-ten alkylthrophenes, gather 3-dodecyl thiophene, gather the 3-bromo thiophene, gather 3, the 4-thioxene, gathers 2; 2 '-two thiophene or gather (3,4-propylene dioxy thiophene).
The present invention compared with prior art has the following advantages:
1, the electrochromic device of the present invention's preparation is flexible, flexible fibrous abnormally-structured; Different with existing plane electrochromic device; Can be used as the more component units of complicated abnormal shape structure devices, and method basis is provided for the assembling of other abnormally-structured device.
2, preparation method's technology of the present invention is simple, can effectively reduce electrochromic device preparation technology's complexity, reduces manufacturing cost, and is expected to prepare the large tracts of land electrochromic device.Through accompanying drawing and embodiment, technical scheme of the present invention is done further detailed description below.
Description of drawings
Fig. 1 is the structural representation of the fibrous flexible electrochromic device of the present invention.
Description of reference numerals:
1-transparent polymer protective seam; 2-filamentary silver is to electrode; 3-polyelectrolyte layer;
4-electrochromic layer; 5-transparency conducting layer; 6-core.
Embodiment
Embodiment 1
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 5% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt hot vapour deposition method to form thickness at core 6 outside surfaces be that the transparent aluminium lamination of 20nm is as transparency conducting layer 5; Said surfactant is a neopelex; The diameter of said core 6 is 0.4mm, and the material of said core 6 is a nylon;
Step 2, employing cladding process will gather (3, the 4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) solution and be coated in formation electrochromic layer 4 on 5 outside surfaces of transparency conducting layer described in the step 1; Said gathering (3, the 4-Ethylenedioxy Thiophene)-gather, the mass concentration of (styrene sulfonic acid) solution was 10%; The thickness of said electrochromic layer 4 is 150nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 outside surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layer 3; The mass percent of said lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 0.5%, 5%, 14.5% and 80%; The thickness of said polyelectrolyte layer 3 is 0.25mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.1mm is positioned in the polyelectrolyte layer described in the step 33 core 6 described in the electrode 2 parallel step 1 with diameter, transparent polymer protective seam 1 be coated on 3 outside surfaces of polyelectrolyte layer described in the step 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 10 μ m, and said transparent polymer protective seam 1 is a polyethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and appear successively from mazarine-transparent change procedure from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
Embodiment 2
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 3% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt hot vapour deposition method to form thickness on core 6 surfaces be that the transparent aluminium lamination of 30nm is as transparency conducting layer 5; Said surfactant is a sodium hexadecyl sulfate; The diameter of said core 6 is 4mm, and the material of said core 6 is a polypropylene;
Step 2, adopt the solution czochralski method, the core 6 that will have a transparency conducting layer 6 is put into polyaniline watersoluble dispersion and is lifted, and on transparency conducting layer described in the step 15, forms electrochromic layer 4; The mass concentration of said polyaniline watersoluble dispersion is 2%; The thickness of said electrochromic layer 4 is 250nm;
Step 3, LiBF4, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layers 3; The mass percent of said LiBF4, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 20% and 70%; The thickness of said polyelectrolyte layer 3 is 0.35mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.2mm is positioned in the polyelectrolyte layer described in the step 33 electrode 2 parallel cores 6 with diameter, transparent polymer protective seam 1 be coated on the polyelectrolyte layer 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 25 μ m, and said transparent polymer protective seam 1 is a polychloroethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and appear successively from yellowish-green-sapphire change procedure from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
Embodiment 3
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 4% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt the ion sputtering method to form thickness on core 6 surfaces be that the transparent gold layer of 40nm is as transparency conducting layer 5; Said surfactant is a sodium cetanesulfonate; The diameter of said core 6 is 2mm, and the material of said core 6 is a tygon.
Step 2, employing electrodeposition process directly form electrochromic layer 4 with polypyrrole through electrochemical polymerization method on transparency conducting layer described in the step 15; The thickness of said electrochromic layer 4 is 200nm;
Step 3, lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layers 3; The mass percent of said lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 4%, 1%, 10% and 85%; The thickness of said polyelectrolyte layer 3 is 0.25mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.15mm is positioned in the polyelectrolyte layer described in the step 33 electrode 2 parallel cores 6 with diameter, transparent polymer protective seam 1 be coated on the polyelectrolyte layer 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 30 μ m, and said transparent polymer protective seam 1 is a polychloroethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and appear successively from yellowish green-hepatic change procedure from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
Embodiment 4
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 4% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt the ion sputtering method to form thickness on core 6 surfaces be that the transparent gold layer of 40nm is as transparency conducting layer 5; Surfactant is the cetyl benzene sulfonic acid sodium salt; The diameter of said core 6 is 2mm, and the material of said core 6 is a tygon.
Step 2, employing electrodeposition process will gather (3,4-ethylene dioxy pyrroles) and directly on transparency conducting layer described in the step 15, form electrochromic layer 4 through electrochemical polymerization method; The thickness of said electrochromic layer 4 is 200nm;
Step 3, lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layers 3; The mass percent of said lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 4%, 1%, 10% and 85%; The thickness of said polyelectrolyte layer 3 is 0.25mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.15mm is positioned in the polyelectrolyte layer described in the step 33 electrode 2 parallel cores 6 with diameter, transparent polymer protective seam 1 be coated on the polyelectrolyte layer 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 30 μ m, and said transparent polymer protective seam 1 is a polychloroethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and appear successively from redness-sapphire change procedure from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
Embodiment 5
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 3% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt the ion sputtering method to form thickness on core 6 surfaces be that the transparent platinum layer of 25nm is as transparency conducting layer 5; Said surfactant is the octadecyl sodium sulfonate; The diameter of said core 6 is 3mm, and the material of said core 6 is a PVC.
Step 2, employing electrodeposition process directly form electrochromic layer 4 with polythiophene through electrochemical polymerization method on transparency conducting layer described in the step 15; The thickness of said electrochromic layer 4 is 220nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layers 3; The mass percent of said lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 5% and 85%; The thickness of said polyelectrolyte layer 3 is 0.3mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.2mm is positioned in the polyelectrolyte layer described in the step 33 electrode 2 parallel cores 6 with diameter, transparent polymer protective seam 1 be coated on the polyelectrolyte layer 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 20 μ m, and said transparent polymer protective seam 1 is a polyethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and present the change procedure from redness-blueness successively from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
Embodiment 6
The fibrous flexible electrochromic device of present embodiment; Comprise core 6; The outside surface of said core 6 is provided with transparency conducting layer 5, and the outside surface of said transparency conducting layer 5 is provided with electrochromic layer 4, and the outside surface of said electrochromic layer 4 is provided with polyelectrolyte layer 3; The outside surface of said polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with said core 6 in the said polyelectrolyte layer 3 to electrode 2.
The fibrous flexible electrochromism preparation of devices method of present embodiment may further comprise the steps:
Step 1, to adopt mass concentration successively be 3% surfactant and washed with de-ionized water core 6 surfaces; Core 6 oven dry after will cleaning then, waiting to dry the back, to adopt the ion sputtering method to form thickness on core 6 surfaces be that the transparent platinum layer of 25nm is as transparency conducting layer 5; Said surfactant is a lauryl sodium sulfate; The diameter of said core 6 is 3mm, and the material of said core 6 is a PVC.
Step 2, employing electrodeposition process will gather 3-dodecyl thiophene and directly on transparency conducting layer described in the step 15, form electrochromic layer 4 through electrochemical polymerization method; The thickness of said electrochromic layer 4 is 220nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on 4 surfaces of electrochromic layer described in the step 2 and form polyelectrolyte layers 3; The mass percent of said lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 5% and 85%; The thickness of said polyelectrolyte layer 3 is 0.3mm; Said polyelectrolyte layer 3 is the gel state polyelectrolyte layer;
Step 4, be that the filamentary silver of 0.2mm is positioned in the polyelectrolyte layer described in the step 33 electrode 2 parallel cores 6 with diameter, transparent polymer protective seam 1 be coated on the polyelectrolyte layer 3 and through heat-seal process obtain fibrous flexible electrochromic device (as shown in Figure 1) then; The thickness of said transparent polymer protective seam 1 is 20 μ m, and said transparent polymer protective seam 1 is a polyethylene film.
The fibrous flexible electrochromic device that present embodiment makes links to each other two leads to electrode with filamentary silver respectively earlier in use with transparency conducting layer, then two leads are connected on the constant voltage dc source.The volt-ampere loop test shows that current potential, can be observed the device color and appear successively from orange-blue change procedure from-2V to the 2V change procedure.15 circulations of accordion seek, device color are obviously decay not.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every technical spirit changes any simple modification, change and the equivalence that above embodiment did according to the present invention, all still belongs in the protection domain of technical scheme of the present invention.

Claims (10)

1. fibrous flexible electrochromic device; It is characterized in that; Comprise core (6); The outside surface of said core (6) is provided with transparency conducting layer (5), and the outside surface of said transparency conducting layer (5) is provided with electrochromic layer (4), and the outside surface of said electrochromic layer (4) is provided with polyelectrolyte layer (3); The outside surface of said polyelectrolyte layer (3) is provided with transparent polymer protective seam (1), is provided with the filamentary silver parallel with said core (6) in the said polyelectrolyte layer (3) to electrode (2); Serve as reasons lithium salts, polymethylmethacrylate, carbonic allyl ester and the acetonitrile of following mass percent of said polyelectrolyte layer (3) mixes the gel state polyelectrolyte layer of processing: lithium salts 0.5%~5%; Polymethylmethacrylate 1%~5%; Carbonic allyl ester 5%~20%; Acetonitrile 70%~85%, wherein said lithium salts are lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
2. a kind of fibrous flexible electrochromic device according to claim 1 is characterized in that the thickness of said transparent polymer protective seam (1) is 10 μ m~30 μ m, and said transparent polymer protective seam (1) is polyethylene film or polychloroethylene film; Said filamentary silver is 0.1mm~0.2mm to the diameter of electrode (2).
3. a kind of fibrous flexible electrochromic device according to claim 1 is characterized in that the thickness of said polyelectrolyte layer (3) is 0.25mm~0.35mm.
4. a kind of fibrous flexible electrochromic device according to claim 1; It is characterized in that; The thickness of said electrochromic layer (4) is 150nm~250nm, and the material of said electrochromic layer (4) is for gathering (3, the 4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) or polyaniline; Or polypyrrole and derivant thereof, or polythiophene and derivant thereof; Said polypyrrole derivant is for gathering (3; 4-ethylene dioxy pyrroles), gather (3; 4-propylene dioxy pyrroles) or poly-methyl pyrrole, said polythiofuran derivative is for gathering 3 methyl thiophene, gather 3-ten alkylthrophenes, gather 3-dodecyl thiophene, gather the 3-bromo thiophene, gather 3, the 4-thioxene, gathers 2; 2 '-two thiophene or gather (3,4-propylene dioxy thiophene).
5. a kind of fibrous flexible electrochromic device according to claim 1 is characterized in that, said transparency conducting layer (5) is that thickness is aluminium lamination, gold layer or the platinum layer of 20nm~40nm.
6. a kind of fibrous flexible electrochromic device according to claim 1 is characterized in that the diameter of said core (6) is 0.4mm~4mm, and the material of said core (6) is nylon, polypropylene, tygon or PVC.
7. one kind prepares the method for fibrous flexible electrochromic device according to claim 1, it is characterized in that this method may further comprise the steps:
Step 1, adopt surfactant and washed with de-ionized water core (6) outside surface successively; Core (6) oven dry after will cleaning is then waited to dry the back and is adopted hot vapour deposition method or ion sputtering method on core (6) outside surface, to form transparent metal layer as transparency conducting layer (5); The mass concentration of said surfactant≤5%, said surfactant are neopelex, cetyl benzene sulfonic acid sodium salt, octadecyl benzene sulfonic acid sodium salt, lauryl sodium sulfate, sodium hexadecyl sulfate, sodium dodecylsulphonate, sodium cetanesulfonate or octadecyl sodium sulfonate;
Step 2, employing cladding process, solution czochralski method or electrodeposition process form electrochromic layer (4) on transparency conducting layer described in the step 1 (5) outside surface;
Step 3, lithium salts, polymethylmethacrylate, carbonic allyl ester and acetonitrile mixed after, be coated on electrochromic layer described in the step 2 (4) outside surface and form polyelectrolyte layer (3);
Step 4, filamentary silver is positioned in the polyelectrolyte layer described in the step 3 (3) electrode (2), transparent polymer protective seam (1) is coated on polyelectrolyte layer described in the step 3 (3) outside surface and through heat-seal process obtains fibrous flexible electrochromic device then.
8. method according to claim 7 is characterized in that, when transparent metal layer described in the step 1 was aluminium lamination, hot vapour deposition method was adopted in the preparation of said transparent metal layer; When transparent metal layer described in the step 1 was gold layer or platinum layer, the ion sputtering method was adopted in the preparation of said transparent metal layer.
9. method according to claim 7; It is characterized in that; Cladding process described in the step 2 is: will gather (3; The 4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) solution or polyaniline watersoluble dispersion is coated on transparency conducting layer (5) outside surface that has core (6) in the step 1, said gathering (3, the 4-Ethylenedioxy Thiophene)-gather the mass concentration of (styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion is 2%~10%; The czochralski method of solution described in the step 2 is: the transparency conducting layer that has core (6) in the step 1 (5) is put into gathered (3; The 4-Ethylenedioxy Thiophene)-gather in (styrene sulfonic acid) solution or the polyaniline watersoluble dispersion and lift; Said gathering (3, the 4-Ethylenedioxy Thiophene)-gather the mass concentration of (styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion is 2%~10%.
10. method according to claim 7; It is characterized in that electrodeposition process described in the step 2 is: with polypyrrole and derivant thereof or polythiophene and derivant thereof through electrochemical polymerization method directly on transparency conducting layer described in the step 1 (5) outside surface polymerization form electrochromic layer (4) described in the step 2; Said polypyrrole derivant is for gathering (3; 4-ethylene dioxy pyrroles), gather (3; 4-propylene dioxy pyrroles) or poly-methyl pyrrole, said polythiofuran derivative is for gathering 3 methyl thiophene, gather 3-ten alkylthrophenes, gather 3-dodecyl thiophene, gather the 3-bromo thiophene, gather 3, the 4-thioxene, gathers 2; 2 '-two thiophene or gather (3,4-propylene dioxy thiophene).
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