CN102759835B - Fiber-shaped flexible electrochromic device and preparation method thereof - Google Patents

Abstract

The invention discloses a fibrous flexible electrochromic device, which comprises a transparent polymer protective layer, a silver wire counter electrode, an electrochromic layer, a transparent conductive layer and a core material. The invention also discloses a method for preparing a fibrous flexible electrochromic device. The method includes the following steps: forming a transparent conductive layer on the surface of the core material by thermal evaporation or ion sputtering; The electrochromic layer is formed on the surface of the transparent conductive layer by pulling method or electrodeposition method; the gel polyelectrolyte is coated on the surface of the electrochromic layer to form a polyelectrolyte layer; the parallel core material of the silver wire opposite electrode is placed on the polyelectrolyte layer In the process, a transparent polymer protective layer is coated on the outer surface of the polyelectrolyte layer and heat-sealed to obtain the device. The process of the invention is simple, and the prepared fibrous flexible electrochromic device is a flexible and bendable fibrous special-shaped structure, which can be used as a component unit of more complex special-shaped structure devices, and provides a method basis for the assembly of other special-shaped structure devices.

Description

A fibrous flexible electrochromic device and its preparation method

technical field

The invention belongs to the technical field of electrochromic devices, and in particular relates to a fibrous flexible electrochromic device and a preparation method thereof.

Background technique

The optical properties (color, transparency, reflectivity, etc.) of electrochromic materials can be reversibly changed under an applied electric field. Due to the characteristics of low operating voltage, no need for backlight, low energy consumption, low cost, and the ability to produce large-area and special-shaped structural devices, electrochromic devices are widely used in display devices, smart windows, military camouflage, and anti-glare automotive rearview mirrors. It has broad application prospects.

Existing electrochromic devices mainly have a sandwich structure, and the sandwich structure is composed of two layers of transparent electrodes, an electrochromic layer and an electrolyte layer sandwiched between the two layers of transparent electrodes. Transparent electrodes mainly include ITO glass and flexible ITO/PET; color-changing materials can be divided into inorganic color-changing materials (the most common such as tungsten trioxide, nickel oxide, molybdenum oxide, and vanadium pentoxide, etc.) and organic color-changing materials. The gain and loss of electrons undergo oxidation-reduction reactions, thereby achieving reversible changes in coloring and fading; the electrolyte layer is usually liquid, gel and solid.

Depending on the electrochromic material and the electrolyte, the performance of the various devices varies. Generally speaking, inorganic color-changing materials have high stability, but the color-changing speed is slow and the processing cost is high; organic color-changing materials have rich colors, fast color changing, easy processing and low driving voltage, save energy, and keep changing color even after power off Effect, with memory function. Liquid electrolyte can give fast response speed, but the device is not easy to package, prone to electrolyte leakage; solid electrolyte is the opposite; relatively speaking, gel electrolyte is widely used because it combines the advantages of both and abandons their respective shortcomings. At present, electrochromic devices have little change in their configuration and structure, and devices with heterogeneous structures are even less.

Contents of the invention

The technical problem to be solved by the present invention is to provide a fibrous flexible electrochromic device with coaxial multi-layer fibrous structure, flexible characteristics and unconventional anisotropic structure for the above-mentioned deficiencies in the prior art.

In order to solve the above technical problems, the technical solution adopted by the present invention is: a fibrous flexible electrochromic device, characterized in that it includes a core material, the outer surface of the core material is provided with a transparent conductive layer, and the transparent conductive layer The outer surface of the electrochromic layer is provided with an electrochromic layer, the outer surface of the electrochromic layer is provided with a polyelectrolyte layer, the outer surface of the polyelectrolyte layer is provided with a transparent polymer protective layer, and the polyelectrolyte layer is placed inside the polyelectrolyte layer. The parallel silver wire counter electrode of the core material; the polyelectrolyte layer is a gel state polyelectrolyte layer made of lithium salt, polymethyl methacrylate, propylene carbonate and acetonitrile mixed in the following mass percentages: Lithium salt 0.5% to 5%, polymethyl methacrylate 1% to 5%, propylene carbonate 5% to 20%, acetonitrile 70% to 85%, wherein the lithium salt is lithium perchlorate, tetrafluoroboric acid lithium or lithium hexafluorophosphate.

The above-mentioned fibrous flexible electrochromic device is characterized in that, the thickness of the transparent polymer protective layer is 10 μm to 30 μm, and the transparent polymer protective layer is a polyethylene film or a polyvinyl chloride film; the silver The diameter of the wire counter electrode is 0.1mm-0.2mm.

The above-mentioned fibrous flexible electrochromic device is characterized in that the polyelectrolyte layer has a thickness of 0.25 mm to 0.35 mm.

The aforementioned fibrous flexible electrochromic device is characterized in that the thickness of the electrochromic layer is 150nm to 250nm, and the material of the electrochromic layer is poly(3,4-ethylenedioxy basethiophene)-poly(styrenesulfonic acid) or polyaniline, or polypyrrole and its derivatives, or polythiophene and its derivatives; the polypyrrole derivatives are poly(3,4-ethylenedioxypyrrole), Poly(3,4-propylenedioxypyrrole) or polymethylpyrrole, the polythiophene derivatives are poly-3-methylthiophene, poly-3-decylthiophene, poly-3-dodecylthiophene, poly-3 - bromothiophene, poly-3,4-dimethylthiophene, poly-2,2'-dithiophene or poly(3,4-propylenedioxythiophene).

The above-mentioned fibrous flexible electrochromic device is characterized in that the transparent conductive layer is an aluminum layer, a gold layer or a platinum layer with a thickness of 20nm-40nm.

The above-mentioned fibrous flexible electrochromic device is characterized in that the diameter of the core material is 0.4mm-4mm, and the material of the core material is nylon, polypropylene, polyethylene or polyvinyl chloride.

The present invention also provides a method for preparing a fibrous flexible electrochromic device, characterized in that the method comprises the following steps:

Step 1. Clean the surface of the core material with surfactant and deionized water in sequence, then dry the cleaned core material, and after drying, use thermal evaporation or ion sputtering to form a transparent metal on the outer surface of the core material. layer as a transparent conductive layer; the mass concentration of the surfactant is ≤5%, and the surfactant is sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, sodium octadecylbenzenesulfonate , Sodium Lauryl Sulfate, Sodium Cetyl Sulfate, Sodium Lauryl Sulfonate, Sodium Cetyl Sulfonate or Sodium Octadecyl Sulfonate;

Step 2, forming an electrochromic layer on the outer surface of the transparent conductive layer described in step 1 by coating method, solution pulling method or electrodeposition method;

Step 3. After mixing the lithium salt, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, coat the outer surface of the electrochromic layer described in step 2 to form a polyelectrolyte layer;

Step 4. Place the silver wire counter electrode in the polyelectrolyte layer described in step 3, and then coat the transparent polymer protective layer on the outer surface of the polyelectrolyte layer described in step 3 and obtain a fibrous flexible Electrochromic devices.

The above-mentioned preparation method of a fibrous flexible electrochromic device is characterized in that, when the transparent metal layer in step 1 is an aluminum layer, the preparation of the transparent metal layer adopts a thermal evaporation method; When the transparent metal layer is a gold layer or a platinum layer, the transparent metal layer is prepared by an ion sputtering method.

The above-mentioned preparation method of a fibrous flexible electrochromic device is characterized in that the coating method described in step 2 is: poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid ) solution or polyaniline aqueous dispersion is coated on the outer surface of the transparent conductive layer with the core material in step one, the poly (3,4-ethylenedioxythiophene)-poly (styrenesulfonic acid) solution The mass concentration of the mass concentration and the mass concentration of the polyaniline aqueous dispersion are both 2% to 10%; the solution pulling method described in step 2 is: the transparent conductive layer with the core material in step 1 is put into poly(3,4 -ethylenedioxythiophene)-poly(styrenesulfonic acid) solution or polyaniline aqueous dispersion for pulling; the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid ) solution and the polyaniline aqueous dispersion have a mass concentration of 2% to 10%.

The above-mentioned method for preparing a fibrous flexible electrochromic device is characterized in that, the electrodeposition method described in step 2 is: polypyrrole and its derivatives or polythiophene and its derivatives are directly deposited on the The electrochromic layer is formed by polymerization on the transparent conductive layer; the polypyrrole derivative is poly(3,4-ethylenedioxypyrrole), poly(3,4-propylenedioxypyrrole) or polymethylpyrrole, and the polypyrrole derivative is Thiophene derivatives are poly-3-methylthiophene, poly-3-decylthiophene, poly-3-dodecylthiophene, poly-3-bromothiophene, poly-3,4-dimethylthiophene, poly-2,2' - dithiophene or poly(3,4-propylenedioxythiophene).

Compared with the prior art, the present invention has the following advantages:

1. The electrochromic device prepared by the present invention is a flexible and bendable fibrous special-shaped structure, which is different from the existing planar electrochromic device. Assembly provides the basis of the method.

2. The preparation method of the present invention has a simple process, can effectively reduce the complexity of the preparation process of electrochromic devices, reduce manufacturing costs, and is expected to prepare large-area electrochromic devices. The technical solutions of the present invention will be described in further detail below with reference to the accompanying drawings and embodiments.

Description of drawings

Fig. 1 is a schematic structural view of the fibrous flexible electrochromic device of the present invention.

Explanation of reference signs:

1—transparent polymer protective layer; 2—silver wire counter electrode; 3—polyelectrolyte layer;

4—Electrochromic layer; 5—Transparent conductive layer; 6—Core material.

Detailed ways

Example 1

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1, using a mass concentration of 5% surfactant and deionized water to clean the surface of the core material 6 successively, then drying the cleaned core material 6, and applying thermal evaporation to the outer surface of the core material 6 after drying. Form a transparent aluminum layer with a thickness of 20nm as the transparent conductive layer 5; the surfactant is sodium dodecylbenzenesulfonate; the diameter of the core material 6 is 0.4mm, and the material of the core material 6 is nylon;

Step 2: Coating the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) solution on the outer surface of the transparent conductive layer 5 described in step 1 to form electrochromism by using a coating method Layer 4; the mass concentration of the poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) solution is 10%; the thickness of the electrochromic layer 4 is 150nm;

Step 3. After mixing lithium perchlorate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it to the outer surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; The mass percentages of lithium acid lithium, polymethyl methacrylate, propylene carbonate and acetonitrile are 0.5%, 5%, 14.5% and 80% respectively; the thickness of the polyelectrolyte layer 3 is 0.25mm; the polyelectrolyte layer 3 is a gel polyelectrolyte layer;

Step 4. Place the silver wire counter electrode 2 with a diameter of 0.1 mm in parallel with the core material 6 described in step 1 in the polyelectrolyte layer 3 described in step 3, and then wrap the transparent polymer protective layer 1 in step 3 The outer surface of the polyelectrolyte layer 3 is heat-sealed to obtain a fibrous flexible electrochromic device (as shown in Figure 1); the thickness of the transparent polymer protective layer 1 is 10 μm, and the transparent polymer protective layer 1 is a polyethylene film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from dark blue to transparent in turn. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

Example 2

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1. Use a surfactant with a mass concentration of 3% and deionized water to clean the surface of the core material 6 in sequence, then dry the cleaned core material 6, and then use a thermal evaporation method to form on the surface of the core material 6 after drying. A transparent aluminum layer with a thickness of 30nm is used as the transparent conductive layer 5; the surfactant is sodium cetyl sulfate; the diameter of the core material 6 is 4mm, and the material of the core material 6 is polypropylene;

Step 2, using the solution pulling method, putting the core material 6 with the transparent conductive layer 6 into the polyaniline aqueous dispersion for pulling, and forming an electrochromic layer 4 on the transparent conductive layer 5 described in step 1; The mass concentration of the polyaniline aqueous dispersion is 2%; the thickness of the electrochromic layer 4 is 250nm;

Step 3. After mixing lithium tetrafluoroborate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it on the surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; the tetrafluoroboric acid The mass percentages of lithium, polymethyl methacrylate, propylene carbonate and acetonitrile are 5%, 5%, 20% and 70% respectively; the thickness of the polyelectrolyte layer 3 is 0.35mm; the polyelectrolyte layer 3 is gel polyelectrolyte layer;

Step 4, place the parallel core material 6 of the silver wire counter electrode 2 with a diameter of 0.2 mm in the polyelectrolyte layer 3 described in step 3, then wrap the transparent polymer protective layer 1 on the polyelectrolyte layer 3 and heat The fibrous flexible electrochromic device (as shown in FIG. 1 ) was obtained through sealing treatment; the thickness of the transparent polymer protective layer 1 was 25 μm, and the transparent polymer protective layer 1 was a polyvinyl chloride film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from light yellow-green-sky blue in sequence. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

Example 3

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1, using a surfactant with a mass concentration of 4% and deionized water to clean the surface of the core material 6 in sequence, then drying the cleaned core material 6, and then using the ion sputtering method to form on the surface of the core material 6 after drying. A transparent gold layer with a thickness of 40 nm is used as the transparent conductive layer 5; the surfactant is sodium hexadecylsulfonate; the diameter of the core material 6 is 2 mm, and the material of the core material 6 is polyethylene.

Step 2, using an electrodeposition method to directly form an electrochromic layer 4 on the transparent conductive layer 5 described in step 1 by using polypyrrole through an electrochemical polymerization method; the thickness of the electrochromic layer 4 is 200 nm;

Step 3. After mixing lithium hexafluorophosphate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it on the surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; the lithium hexafluorophosphate, polymethacrylic acid The mass percentages of methyl ester, propylene carbonate and acetonitrile are 4%, 1%, 10% and 85% respectively; the thickness of the polyelectrolyte layer 3 is 0.25mm; the polyelectrolyte layer 3 is a gel polyelectrolyte layer ;

Step 4, place the parallel core material 6 of the silver wire counter electrode 2 with a diameter of 0.15 mm in the polyelectrolyte layer 3 described in step 3, then wrap the transparent polymer protective layer 1 on the polyelectrolyte layer 3 and heat The fibrous flexible electrochromic device (as shown in FIG. 1 ) was obtained through sealing treatment; the thickness of the transparent polymer protective layer 1 is 30 μm, and the transparent polymer protective layer 1 is a polyvinyl chloride film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from yellow-green to blue-purple in sequence. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

Example 4

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1, using a surfactant with a mass concentration of 4% and deionized water to clean the surface of the core material 6 in sequence, then drying the cleaned core material 6, and then using the ion sputtering method to form on the surface of the core material 6 after drying. A transparent gold layer with a thickness of 40 nm is used as the transparent conductive layer 5; the surfactant is sodium hexadecylbenzene sulfonate; the diameter of the core material 6 is 2 mm, and the material of the core material 6 is polyethylene.

Step 2. Electrodeposition is used to directly form an electrochromic layer 4 on the transparent conductive layer 5 in step 1 by using poly(3,4-ethylenedioxypyrrole) through electrochemical polymerization; the electrochromic layer 4 has a thickness of 200nm;

Step 3. After mixing lithium hexafluorophosphate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it on the surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; the lithium hexafluorophosphate, polymethacrylic acid The mass percentages of methyl ester, propylene carbonate and acetonitrile are 4%, 1%, 10% and 85% respectively; the thickness of the polyelectrolyte layer 3 is 0.25mm; the polyelectrolyte layer 3 is a gel polyelectrolyte layer ;

Step 4, place the parallel core material 6 of the silver wire counter electrode 2 with a diameter of 0.15 mm in the polyelectrolyte layer 3 described in step 3, then wrap the transparent polymer protective layer 1 on the polyelectrolyte layer 3 and heat The fibrous flexible electrochromic device (as shown in FIG. 1 ) was obtained through sealing treatment; the thickness of the transparent polymer protective layer 1 is 30 μm, and the transparent polymer protective layer 1 is a polyvinyl chloride film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from red to sky blue in turn. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

Example 5

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1. Use a surfactant with a mass concentration of 3% and deionized water to clean the surface of the core material 6 in sequence, then dry the cleaned core material 6, and then use the ion sputtering method to form on the surface of the core material 6 after drying. A transparent platinum layer with a thickness of 25 nm is used as the transparent conductive layer 5; the surfactant is sodium octadecylsulfonate; the diameter of the core material 6 is 3 mm, and the material of the core material 6 is polyvinyl chloride.

Step 2, using an electrodeposition method to directly form an electrochromic layer 4 on the transparent conductive layer 5 described in step 1 with polythiophene by electrochemical polymerization; the thickness of the electrochromic layer 4 is 220nm;

Step 3. After mixing lithium perchlorate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it to the surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; the perchloric acid The mass percentages of lithium, polymethyl methacrylate, propylene carbonate and acetonitrile are 5%, 5%, 5% and 85% respectively; the thickness of the polyelectrolyte layer 3 is 0.3mm; the polyelectrolyte layer 3 is gel polyelectrolyte layer;

Step 4, place the parallel core material 6 of the silver wire counter electrode 2 with a diameter of 0.2 mm in the polyelectrolyte layer 3 described in step 3, then wrap the transparent polymer protective layer 1 on the polyelectrolyte layer 3 and heat The fibrous flexible electrochromic device (as shown in FIG. 1 ) was obtained through sealing treatment; the thickness of the transparent polymer protective layer 1 is 20 μm, and the transparent polymer protective layer 1 is a polyethylene film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from red to blue in sequence. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

Example 6

The fibrous flexible electrochromic device of this embodiment includes a core material 6, the outer surface of the core material 6 is provided with a transparent conductive layer 5, and the outer surface of the transparent conductive layer 5 is provided with an electrochromic layer 4, so The outer surface of the electrochromic layer 4 is provided with a polyelectrolyte layer 3, the outer surface of the polyelectrolyte layer 3 is provided with a transparent polymer protective layer 1, and the polyelectrolyte layer 3 is provided with a layer parallel to the core material 6. The silver wire counter electrode 2.

The preparation method of the fibrous flexible electrochromic device of this embodiment comprises the following steps:

Step 1. Use a surfactant with a mass concentration of 3% and deionized water to clean the surface of the core material 6 in sequence, then dry the cleaned core material 6, and then use the ion sputtering method to form on the surface of the core material 6 after drying. A transparent platinum layer with a thickness of 25 nm is used as the transparent conductive layer 5; the surfactant is sodium lauryl sulfate; the diameter of the core material 6 is 3 mm, and the material of the core material 6 is polyvinyl chloride.

Step 2, using the electrodeposition method, directly form the electrochromic layer 4 on the transparent conductive layer 5 described in step 1 by the poly-3-dodecylthiophene by electrochemical polymerization; the thickness of the electrochromic layer 4 220nm;

Step 3. After mixing lithium perchlorate, polymethyl methacrylate, propylene carbonate and acetonitrile evenly, apply it to the surface of the electrochromic layer 4 described in step 2 to form a polyelectrolyte layer 3; the perchloric acid The mass percentages of lithium, polymethyl methacrylate, propylene carbonate and acetonitrile are 5%, 5%, 5% and 85% respectively; the thickness of the polyelectrolyte layer 3 is 0.3mm; the polyelectrolyte layer 3 is gel polyelectrolyte layer;

Step 4, place the parallel core material 6 of the silver wire counter electrode 2 with a diameter of 0.2 mm in the polyelectrolyte layer 3 described in step 3, then wrap the transparent polymer protective layer 1 on the polyelectrolyte layer 3 and heat The fibrous flexible electrochromic device (as shown in FIG. 1 ) was obtained through sealing treatment; the thickness of the transparent polymer protective layer 1 is 20 μm, and the transparent polymer protective layer 1 is a polyethylene film.

When the fibrous flexible electrochromic device prepared in this embodiment is used, two wires are connected to the silver wire counter electrode and the transparent conductive layer respectively, and then the two wires are connected to a regulated DC power supply. The voltammetric cycle test shows that when the potential changes from -2V to 2V, the color of the device can be observed to change from orange to blue in sequence. After 15 cycles of back-and-forth testing, the color of the device has no obvious attenuation.

The above are only preferred embodiments of the present invention, and do not limit the present invention in any way. All simple modifications, changes and equivalent changes made to the above embodiments according to the technical essence of the present invention still belong to the technical solution of the present invention. within the scope of protection.

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).