CN102759835B - Fiber-shaped flexible electrochromic device and preparation method thereof - Google Patents
Fiber-shaped flexible electrochromic device and preparation method thereof Download PDFInfo
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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
Technical field
The invention belongs to electrochromic device technical field, be specifically related to a kind of fibrous flexible electro-chromic device and preparation method thereof.
Background technology
The optical characteristics (color, transparency and reflectivity etc.) of electrochromic material can realize reversible variation under extra electric field.Electrochromic device because operating voltage is low, without backlight, energy consumption is little, cost is low and can produce the feature such as large area 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 mainly taking sandwich structure as main, 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 as 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 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 if also keep color changeable effect after power-off, there is memory function.Liquid electrolyte can give fast response speed, but device is difficult for encapsulation, and electrolyte leakage easily occurs; Solid electrolyte is contrary; Comparatively speaking, gel electrolyte is because the shortcoming of abandoning separately in conjunction with both advantages is widely used.At present, electrochromic device changes very little in its configuration and structure, and abnormally-structured device still less.
Summary of the invention
Technical matters to be solved by this invention is to be for above-mentioned deficiency of the prior art, and a kind of fibrous flexible electro-chromic device with coaxial multi-layer filamentary structure, flexibility characteristics and unconventional different in nature structure is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of fibrous flexible electro-chromic device, it is characterized in that, comprise core, the outside surface of described core is provided with transparency conducting layer, and the outside surface of described transparency conducting layer is provided with electrochromic layer, and the outside surface of described electrochromic layer is provided with polyelectrolyte layer, the outside surface of described polyelectrolyte layer is provided with transparent polymer protective seam, is placed with the filamentary silver parallel with described core to electrode in described polyelectrolyte layer; Described 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 making: lithium salts 0.5%～5%, polymethylmethacrylate 1%～5%, carbonic allyl ester 5%～20%, acetonitrile 70%～85%, wherein said lithium salts is lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
The fibrous flexible electro-chromic device of above-mentioned one, is characterized in that, the thickness of described transparent polymer protective seam is 10 μ m～30 μ m, and described transparent polymer protective seam is polyethylene film or polychloroethylene film; Described filamentary silver is 0.1mm～0.2mm to the diameter of electrode.
The fibrous flexible electro-chromic device of above-mentioned one, is characterized in that, the thickness of described polyelectrolyte layer is 0.25mm～0.35mm.
The fibrous flexible electro-chromic device of above-mentioned one, it is characterized in that, the thickness of described electrochromic layer is 150nm～250nm, the material of described electrochromic layer is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or polyaniline, or polypyrrole and derivant thereof, or polythiophene and derivant thereof; Described Polypyrrole derivatives is poly-(3,4-ethylene dioxy pyrroles), poly-(3,4-propylene dioxy pyrroles) or poly-methyl pyrrole, described polythiofuran derivative is poly-3 methyl thiophene, poly-3-ten alkylthrophenes, poly-3-dodecyl thiophene, poly-3-bromo thiophene, poly-3,4-thioxene, poly-2,2 '-bis-thiophene or poly-(3,4-propylene dioxy thiophene).
The fibrous flexible electro-chromic device of above-mentioned one, is characterized in that, described transparency conducting layer is that thickness is aluminium lamination, gold layer or the platinum layer of 20nm～40nm.
The fibrous flexible electro-chromic device of above-mentioned one, is characterized in that, the diameter of described core is 0.4mm～4mm, and the material of described core is nylon, polypropylene, tygon or Polyvinylchloride.
The present invention also provides a kind of preparation method of fibrous flexible electro-chromic device, it is characterized in that, the method comprises the steps:
Step 1, adopt surfactant and washed with de-ionized water core surface successively, then the core after cleaning is dried, the hot vapour deposition method of rear employing to be dried or ion sputtering method form transparent metal layer as transparency conducting layer on core outside surface; Mass concentration≤5% of described surfactant, described surfactant is 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 step 1;
Step 3, lithium salts, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on the outside surface of electrochromic layer described in step 2 form polyelectrolyte layer;
Step 4, filamentary silver is positioned over described in step 3 in polyelectrolyte layer electrode, then transparent polymer protective seam is coated on the outside surface of polyelectrolyte layer described in step 3 and through heat-seal process and obtains fibrous flexible electro-chromic device.
The preparation method of above-mentioned a kind of fibrous flexible electro-chromic device, is characterized in that, when transparent metal layer described in step 1 is aluminium lamination, the preparation of described transparent metal layer adopts hot vapour deposition method; When transparent metal layer described in step 1 is gold layer or platinum layer, the preparation of described transparent metal layer adopts ion sputtering method.
The preparation method of above-mentioned a kind of fibrous flexible electro-chromic device, it is characterized in that, cladding process described in step 2 is: will gather (3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) solution or polyaniline watersoluble dispersion be coated in step 1 on the transparency conducting layer outside surface with core, described poly-(3,4-Ethylenedioxy Thiophene)-mass concentration of poly-(styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion are 2%～10%; The czochralski method of solution described in step 2 is: the transparency conducting layer with core in step 1 is put in poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) solution or polyaniline watersoluble dispersion and lifted; The mass concentration of described poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) solution and polyaniline watersoluble dispersion is 2%～10%.
The preparation method of above-mentioned a kind of fibrous flexible electro-chromic device, it is characterized in that, electrodeposition process described in step 2 is: by polypyrrole and derivant thereof or polythiophene and derivant thereof by electrochemical polymerization method directly on transparency conducting layer polymerization form electrochromic layer; Described Polypyrrole derivatives is poly-(3,4-ethylene dioxy pyrroles), poly-(3,4-propylene dioxy pyrroles) or poly-methyl pyrrole, described polythiofuran derivative is poly-3 methyl thiophene, poly-3-ten alkylthrophenes, poly-3-dodecyl thiophene, poly-3-bromo thiophene, poly-3,4-thioxene, poly-2,2 '-bis-thiophene or poly-(3,4-propylene dioxy thiophene).
The present invention compared with prior art has the following advantages:
1, the electrochromic device that prepared by the present invention is for flexible, flexible fibrous abnormally-structured, different from existing plane electrochromic device, can be used as the more component units of complicated abnormal shape structure devices, and be the assembling supplying method basis of other abnormally-structured device.
2, preparation method's technique of the present invention is simple, can effectively reduce electrochromic device preparation technology's complexity, reduces manufacturing cost, and is expected to prepare large area electrochromic device.Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is the structural representation of the fibrous flexible electro-chromic 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 electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 5% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent aluminium lamination that the hot vapour deposition method of rear employing to be dried is 20nm at core 6 outside surfaces formation thickness is as transparency conducting layer 5; Described surfactant is neopelex; The diameter of described core 6 is 0.4mm, and the material of described core 6 is nylon;
Step 2, adopt cladding process, will gather (3,4-Ethylenedioxy Thiophene)-gather (styrene sulfonic acid) solution and be coated on the outside surface of transparency conducting layer 5 described in step 1 and form electrochromic layer 4; The mass concentration of described poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) solution is 10%; The thickness of described electrochromic layer 4 is 150nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on the outside surface of electrochromic layer 4 described in step 2 form polyelectrolyte layer 3; The mass percent of described lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 0.5%, 5%, 14.5% and 80%; The thickness of described polyelectrolyte layer 3 is 0.25mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.1mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 core 6 described in the parallel step 1 of electrode 2, then transparent polymer protective seam 1 are coated on the outside surface of polyelectrolyte layer 3 described in step 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 10 μ m, and described transparent polymer protective seam 1 is polyethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from mazarine-transparent change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
Embodiment 2
The fibrous flexible electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 3% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent aluminium lamination that the hot vapour deposition method of rear employing to be dried is 30nm at core 6 surface formation thickness is as transparency conducting layer 5; Described surfactant is sodium hexadecyl sulfate; The diameter of described core 6 is 4mm, and the material of described core 6 is polypropylene;
Step 2, employing solution czochralski method, put into polyaniline watersoluble dispersion by the core with transparency conducting layer 66 and lift, and forms electrochromic layer 4 on transparency conducting layer 5 described in step 1; The mass concentration of described polyaniline watersoluble dispersion is 2%; The thickness of described electrochromic layer 4 is 250nm;
Step 3, LiBF4, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer 4 described in step 2 surface and form polyelectrolyte layer 3; The mass percent of described LiBF4, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 20% and 70%; The thickness of described polyelectrolyte layer 3 is 0.35mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.2mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 the parallel core 6 of electrode 2, then transparent polymer protective seam 1 are coated on polyelectrolyte layer 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 25 μ m, and described transparent polymer protective seam 1 is polychloroethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from yellowish-green-sapphire change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
Embodiment 3
The fibrous flexible electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 4% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent gold layer that it is 40nm that rear employing ion sputtering method to be dried forms thickness on core 6 surfaces is as transparency conducting layer 5; Described surfactant is sodium cetanesulfonate; The diameter of described core 6 is 2mm, and the material of described core 6 is tygon.
Step 2, employing electrodeposition process directly form electrochromic layer 4 by polypyrrole by electrochemical polymerization method on transparency conducting layer 5 described in step 1; The thickness of described electrochromic layer 4 is 200nm;
Step 3, lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer 4 described in step 2 surface and form polyelectrolyte layer 3; The mass percent of described lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 4%, 1%, 10% and 85%; The thickness of described polyelectrolyte layer 3 is 0.25mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.15mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 the parallel core 6 of electrode 2, then transparent polymer protective seam 1 are coated on polyelectrolyte layer 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 30 μ m, and described transparent polymer protective seam 1 is polychloroethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from yellowish green-hepatic change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
Embodiment 4
The fibrous flexible electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 4% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent gold layer that it is 40nm that rear employing ion sputtering method to be dried forms thickness on core 6 surfaces is as transparency conducting layer 5; Surfactant is cetyl benzene sulfonic acid sodium salt; The diameter of described core 6 is 2mm, and the material of described core 6 is tygon.
Step 2, employing electrodeposition process, will gather (3,4-ethylene dioxy pyrroles) and directly on transparency conducting layer 5 described in step 1, form electrochromic layer 4 by electrochemical polymerization method; The thickness of described electrochromic layer 4 is 200nm;
Step 3, lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer 4 described in step 2 surface and form polyelectrolyte layer 3; The mass percent of described lithium hexafluoro phosphate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 4%, 1%, 10% and 85%; The thickness of described polyelectrolyte layer 3 is 0.25mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.15mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 the parallel core 6 of electrode 2, then transparent polymer protective seam 1 are coated on polyelectrolyte layer 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 30 μ m, and described transparent polymer protective seam 1 is polychloroethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from redness-sapphire change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
Embodiment 5
The fibrous flexible electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 3% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent platinum layer that rear employing ion sputtering method to be dried is 25nm at core 6 surface formation thickness is as transparency conducting layer 5; Described surfactant is octadecyl sodium sulfonate; The diameter of described core 6 is 3mm, and the material of described core 6 is Polyvinylchloride.
Step 2, employing electrodeposition process directly form electrochromic layer 4 by polythiophene by electrochemical polymerization method on transparency conducting layer 5 described in step 1; The thickness of described electrochromic layer 4 is 220nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer 4 described in step 2 surface and form polyelectrolyte layer 3; The mass percent of described lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 5% and 85%; The thickness of described polyelectrolyte layer 3 is 0.3mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.2mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 the parallel core 6 of electrode 2, then transparent polymer protective seam 1 are coated on polyelectrolyte layer 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 20 μ m, and described transparent polymer protective seam 1 is polyethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from red-blue change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
Embodiment 6
The fibrous flexible electro-chromic device of the present embodiment; comprise core 6; the outside surface of described core 6 is provided with transparency conducting layer 5; the outside surface of described transparency conducting layer 5 is provided with electrochromic layer 4; the outside surface of described electrochromic layer 4 is provided with polyelectrolyte layer 3; the outside surface of described polyelectrolyte layer 3 is provided with transparent polymer protective seam 1, is provided with the filamentary silver parallel with described core 6 to electrode 2 in described polyelectrolyte layer 3.
The preparation method of the fibrous flexible electro-chromic device of the present embodiment comprises the following steps:
Step 1, to adopt mass concentration be successively 3% surfactant and washed with de-ionized water core 6 surfaces, then the core 6 after cleaning is dried, the transparent platinum layer that rear employing ion sputtering method to be dried is 25nm at core 6 surface formation thickness is as transparency conducting layer 5; Described surfactant is lauryl sodium sulfate; The diameter of described core 6 is 3mm, and the material of described core 6 is Polyvinylchloride.
Step 2, employing electrodeposition process, will gather 3-dodecyl thiophene and directly on transparency conducting layer 5 described in step 1, form electrochromic layer 4 by electrochemical polymerization method; The thickness of described electrochromic layer 4 is 220nm;
Step 3, lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer 4 described in step 2 surface and form polyelectrolyte layer 3; The mass percent of described lithium perchlorate, polymethylmethacrylate, carbonic allyl ester and acetonitrile is respectively 5%, 5%, 5% and 85%; The thickness of described polyelectrolyte layer 3 is 0.3mm; Described polyelectrolyte layer 3 is gel state polyelectrolyte layer;
Step 4, the filamentary silver that is 0.2mm by diameter are positioned in polyelectrolyte layer 3 described in step 3 the parallel core 6 of electrode 2, then transparent polymer protective seam 1 are coated on polyelectrolyte layer 3 and through heat-seal process and obtain fibrous flexible electro-chromic device (as shown in Figure 1); The thickness of described transparent polymer protective seam 1 is 20 μ m, and described transparent polymer protective seam 1 is polyethylene film.
The fibrous flexible electro-chromic device that the present embodiment makes in use, is first connected two wires to electrode with filamentary silver respectively with transparency conducting layer, then two wires are connected on constant voltage dc source.Volt-ampere loop test shows, current potential, can be observed device color and present successively from orange-blue change procedure from-2V to 2V change procedure.15 circulations of accordion seek, device color is obviously decay not.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every any simple modification of above embodiment being done according to the technology of the present invention essence, change and equivalence change, and all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. a fibrous flexible electro-chromic device, comprise core (6), the outside surface of described core (6) is provided with transparency conducting layer (5), the outside surface of described transparency conducting layer (5) is provided with electrochromic layer (4), the outside surface of described electrochromic layer (4) is provided with polyelectrolyte layer (3), it is characterized in that, the outside surface of described polyelectrolyte layer (3) is provided with transparent polymer protective seam (1), is provided with the filamentary silver parallel with described core (6) to electrode (2) in described polyelectrolyte layer (3); Serve as reasons lithium salts, polymethylmethacrylate, carbonic allyl ester and the acetonitrile of following mass percent of described polyelectrolyte layer (3) mixes the gel state polyelectrolyte layer of making: lithium salts 0.5%～5%, polymethylmethacrylate 1%～5%, carbonic allyl ester 5%～20%, acetonitrile 70%～85%, wherein said lithium salts is lithium perchlorate, LiBF4 or lithium hexafluoro phosphate.
2. the fibrous flexible electro-chromic device of one according to claim 1, it is characterized in that, the thickness of described transparent polymer protective seam (1) is 10 μ m～30 μ m, and described transparent polymer protective seam (1) is polyethylene film or polychloroethylene film; Described filamentary silver is 0.1mm～0.2mm to the diameter of electrode (2).
3. the fibrous flexible electro-chromic device of one according to claim 1, is characterized in that, the thickness of described polyelectrolyte layer (3) is 0.25mm～0.35mm.
4. the fibrous flexible electro-chromic device of one according to claim 1, it is characterized in that, the thickness of described electrochromic layer (4) is 150nm～250nm, the material of described electrochromic layer (4) is poly-(3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) or polyaniline, or polypyrrole and derivant thereof, or polythiophene and derivant thereof; Described Polypyrrole derivatives is poly-(3,4-ethylene dioxy pyrroles), poly-(3,4-propylene dioxy pyrroles) or poly-methyl pyrrole, described polythiofuran derivative is poly-3 methyl thiophene, poly-3-ten alkylthrophenes, poly-3-dodecyl thiophene, poly-3-bromo thiophene, poly-3,4-thioxene, poly-2,2 '-bis-thiophene or poly-(3,4-propylene dioxy thiophene).
5. the fibrous flexible electro-chromic device of one according to claim 1, is characterized in that, described transparency conducting layer (5) is that thickness is aluminium lamination, gold layer or the platinum layer of 20nm～40nm.
6. the fibrous flexible electro-chromic device of one according to claim 1, is characterized in that, the diameter of described core (6) is 0.4mm～4mm, and the material of described core (6) is nylon, polypropylene, tygon or Polyvinylchloride.
7. prepare a method for fibrous flexible electro-chromic device as claimed in claim 1, it is characterized in that, the method comprises the following steps:
Step 1, adopt surfactant and washed with de-ionized water core (6) outside surface successively, then the core (6) after cleaning is dried, the hot vapour deposition method of rear employing to be dried or ion sputtering method form transparent metal layer as transparency conducting layer (5) on core (6) outside surface; Mass concentration≤5% of described surfactant, described surfactant is 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 step 1 (5) outside surface;
Step 3, lithium salts, polymethylmethacrylate, carbonic allyl ester and acetonitrile are mixed after, be coated on electrochromic layer described in step 2 (4) outside surface form polyelectrolyte layer (3);
Step 4, filamentary silver is positioned in polyelectrolyte layer described in step 3 (3) electrode (2), then transparent polymer protective seam (1) is coated on polyelectrolyte layer described in step 3 (3) outside surface and obtains fibrous flexible electro-chromic device through heat-seal process.
8. method according to claim 7, is characterized in that, when transparent metal layer described in step 1 is aluminium lamination, the preparation of described transparent metal layer adopts hot vapour deposition method; When transparent metal layer described in step 1 is gold layer or platinum layer, the preparation of described transparent metal layer adopts ion sputtering method.
9. method according to claim 7, it is characterized in that, cladding process described in step 2 is: will gather (3,4-Ethylenedioxy Thiophene)-poly-(styrene sulfonic acid) solution or polyaniline watersoluble dispersion be coated in step 1 on transparency conducting layer (5) outside surface with core (6), described poly-(3,4-Ethylenedioxy Thiophene)-mass concentration of poly-(styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion are 2%～10%; The czochralski method of solution described in step 2 is: the transparency conducting layer (5) with core (6) in step 1 is put into poly-(3,4-Ethylenedioxy Thiophene) lift in-poly-(styrene sulfonic acid) solution or polyaniline watersoluble dispersion, described poly-(3,4-Ethylenedioxy Thiophene)-mass concentration of poly-(styrene sulfonic acid) solution and the mass concentration of polyaniline watersoluble dispersion are 2%～10%.
10. method according to claim 7, it is characterized in that, electrodeposition process described in step 2 is: by polypyrrole and derivant thereof or polythiophene and derivant thereof by electrochemical polymerization method directly on transparency conducting layer described in step 1 (5) outside surface polymerization form electrochromic layer (4) described in step 2; Described Polypyrrole derivatives is poly-(3,4-ethylene dioxy pyrroles), poly-(3,4-propylene dioxy pyrroles) or poly-methyl pyrrole, described polythiofuran derivative is poly-3 methyl thiophene, poly-3-ten alkylthrophenes, poly-3-dodecyl thiophene, poly-3-bromo thiophene, poly-3,4-thioxene, poly-2,2 '-bis-thiophene or poly-(3,4-propylene dioxy thiophene).
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