CN1949070A - Reflecting type whole solid paper loading electrochromism device and preparation method thereof - Google Patents

Abstract

The invention relates to a reflective all-solid-state electrochromic device with paper as a carrier material and a preparation method thereof. The device includes a paper-supported electrochromic layer, an ion conductor layer made of polymer solid or gel-type polyelectrolyte, an organic or inorganic counter electrode layer that is an ion storage layer, a conductive electrode layer and a transparent glass substrate layer. The electrochromic device is based on the paper-carried electrochromic layer as the main display film. The two sides of the paper-carried electrochromic layer are tightly pressed with the ion conductor layer made of polymer solid or gel-type polyelectrolyte. The ion conductor layer on both sides is In order to have a conductive electrode layer and a transparent glass base layer respectively, the sides of the above layers are sealed and packaged together and connected with electrodes. This device can not only greatly improve the contrast of the device, but also adopts the pixel partition isolation technology on the paper carrier and the electrode simultaneously, which can overcome the problems of "crosstalk phenomenon", "pixel discrete", leakage, image blur, etc., combined with modern printing technology and automatic processing , it is possible to obtain low-cost electrochromic displays, which will lay a solid foundation for the commercialization and popularization of electrochromic electronic ink and electronic paper, and lay a solid foundation for color electrochromic displays.

Description

Reflective all-solid-state paper-mounted electrochromic device and preparation method thereof

technical field

The invention relates to an electrochromic device, in particular to a reflective all-solid-state electrochromic device using paper as a carrier material.

technical background

Electrochromism (EC) refers to the phenomenon that the optical properties of materials produce stable and reversible changes under the action of an external electric field. In terms of appearance properties, it is manifested as reversible changes in color and transparency. As early as the 1930s, there were reports on electrochromic phenomena. In 1969, SKDeb first used amorphous WO ₃ thin films to make electrochromic devices, and proposed the "oxygen vacancy color center mechanism". Since then, people have gradually realized the unique advantages and potential application prospects of electrochromism. Electrochromic materials and electrochromic devices have broad application prospects in the fields of photoelectric energy conversion, light intensity adjustment, information recording, and large-screen display. In the 1970s, a large number of reports on the electrochromic mechanism and inorganic color-changing materials appeared. In addition to transition metal oxides such as WO ₃ , electrochromic materials such as heteropolyacids and Prussian blue also appeared. Since the end of the 1980s, research on electrochromic materials, including organic electrochromic materials and electrochromic devices, has become increasingly active. Only the US Patent Office has granted more than 600 related patents. The smart energy-saving window proposed by C M Lampert has been It is considered a milestone in electrochromic research. In recent years, electrochromic devices have gradually been commercialized. For example, devices using tungsten trioxide and 4,4'-bipyridylium salts, namely viologen derivatives, as electrochromic materials are used in millions of automobiles every year. In the shading mirror. Electrochromic energy-saving smart windows and automotive rearview anti-glare mirrors have also been successfully developed into commercial devices. The most attractive thing about electrochromic materials and electrochromic devices is the application of their low energy consumption display performance, especially in the fields of low energy consumption flat panel display, large screen display and portable display.

The use of paper has a history of nearly 2,000 years, and paper is still the most widely used medium for cultural communication. According to statistics, the world produces and consumes more than 300 million tons of paper every year, which is equivalent to destroying billions of adult trees that have grown for decades, and the growth of paper consumption continues. However, the mass production and consumption of paper and the flooding of printed materials consume a large amount of forest resources, chemicals and energy, causing serious pollution to the environment, and the advantages of electronic paper, digital paper or paper display with low energy consumption and rewritable rewritable just overcome these shortcomings. The key technology of electronic paper is electronic ink. Microcapsule electrophoretic electronic ink is the earliest and most mature electronic ink technology studied, and has been commercialized through more than ten years of hard work by companies such as E-INK and Philips in the United States. However, the technology is difficult, the yield rate is low, and the price is high. For example, the AM-100 6-inch electronic paper display standard prototype of the American E-INK company has a sales price of 3,000 US dollars, which is equivalent to nearly 24,000 yuan in RMB. For ordinary families, this is simply a sky-high price. Guangzhou Jinchan Software R&D Center sells Philips’ 10-inch Dr. Yi-ILIAD handwriting computer in China, which is also E-INK’s electronic paper technology. The price of this product is RMB 8,000 for English display and RMB 9,000 for Chinese display Yuan, this price is also difficult for ordinary families to accept. At present, E-INK's microcapsule electrophoretic electronic ink and electronic paper technology are in a dilemma. On the one hand, many foreign companies such as E-INK have spent a lot of manpower, material resources, and financial resources after years of struggle. The price has dropped to a price that can be widely accepted by ordinary families. On the other hand, it will cost more manpower, material resources, and financial resources to develop new technologies. Electrochromic (EC) display combined with nanotechnology is the lowest-cost electronic ink display technology developed in recent years.

The use of electrochromic as a display device, including several basic elements of electronic ink, has been basically achieved after years of efforts. For example, viologen compounds and their polymers and copolymers have excellent electrochromic properties, including extremely high coloring efficiency, and a fast discoloration response time of tens of milliseconds, and only 1-3 volts are required for extremely low discoloration Driving voltage, more than ten million times of color-bleaching-color cycle as a cycle life of color change, especially excellent stability, the open-circuit memory after color change can maintain more than ten years without fading.

However, due to the high sensitivity of electrochromic materials to small current and voltage, problems such as "crosstalk phenomenon" and "pixel discreteness" will appear in the process of fixed-point display and addressing display, which will make the pixel display leak and the image blurred. Although the international patent PCT/US2002/008594 applied by Dow Global Technology Corporation of the United States and the US patents US 4,129,861, US 4,488,781, and US 5,189,549 previously applied by other companies are trying to overcome or solve the problems of "crosstalk phenomenon" and "pixel discrete", However, the cost and complexity of electrochromic devices are often increased, and it is difficult to completely overcome these technical obstacles.

Contents of the invention

In order to solve the above-mentioned problems of using electrochromic as a display device, the present invention provides a reflective all-solid-state paper-mounted electrochromic device with simple process and low cost and a preparation method thereof.

The reflective all-solid-state paper-mounted electrochromic device proposed by the invention includes a paper-mounted electrochromic layer, an ion conductor layer made of polymer solid or gel-type polyelectrolyte, a conductive electrode layer and a transparent glass base layer. The main difference between the present invention and other electrochromic devices is that the paper is used as the carrier of the electrochromic material, and the paper-carried electrochromic layer is used as the main color-developing film of the electrochromic display device. Both sides of the paper-borne electrochromic layer are tightly pressed with the ion conductor layer made of polymer solid or gel polyelectrolyte. The ion conductor layer on one side has a conductive electrode layer and a transparent glass substrate layer, and the ion conductor layer on the other side There are also conductive electrode layers and transparent glass substrate layers on the conductor layer, so that the paper-borne electrochromic layer and the solid or gel-state ionic conductor layer are placed in an ordinary all-solid-state electrochromic device instead of the electrochromic film layer. The sides of the above-mentioned layers are jointly sealed and packaged and connected with electrodes.

Further, an organic or inorganic counter electrode layer, that is, an ion storage layer, may also be provided between the ion conductor layer and the conductive electrode layer and the transparent glass substrate layer thereon.

The above conductive electrode layer and transparent glass base layer can directly use commercially available ITO conductive glass. It is required that the light transmittance in the visible light wavelength range is 70-100%, preferably more than 80%, and the square resistivity is below 300Ω·cm. Under the premise of ensuring high light transmittance, the square of the transparent conductive substrate The smaller the resistivity, the better.

The above-mentioned paper-supported electrochromic layer is made of paper as the carrier of the electrochromic material, and the solution or suspension of the electrochromic material is uniformly coated on the paper by coating method, dipping method, spraying method or printing method, and vacuum dried Obtained after removal of solvent. The paper can be commercially available in various types and grades of white mechanism or hand-made printing paper, copy paper, writing paper or calligraphy and painting paper, used directly or printed small grids on the paper with adhesive ink or printing ink for partitioning Used after grid processing.

The electrochromic material loaded on the paper used in the present invention can be an inorganic or organic electrochromic material, and the inorganic electrochromic material is usually a transition metal oxide such as WO ₃ , MoO ₃ , TiO ₂ , Nb ₂ O ₅ , V ₂ O ₅ , etc. one or more doped. One or several doped ultrafine powders and nanopowders of these transition metal oxides can be used to disperse in organic solvents such as ethanol, acetone, ethyl acetate or aqueous solutions containing organic solvents, and add a certain amount of dispersant and stabilizer , viscose, film-forming agent, etc. are formulated into suspension dip-coating materials, which are evenly coated and loaded on paper by coating, dipping, spraying or printing methods. A layer of electrochromic material, but preferably requires coating, spraying or printing on both sides of the paper.

Organic electrochromic materials loaded on paper include various derivatives, polymers, and copolymers of viologen, that is, 4,4'-bipyridine, various derivatives, polymers, and copolymers of metal phthalocyanine, Derivatives and copolymers of polyaniline, derivatives and copolymers of polythiophene, derivatives and copolymers of polypyrrole, polymeric metal complexes containing organic ligands, Prussian blue, etc. According to the form of these organic electrochromic materials, they are prepared as corresponding solutions or suspensions, which are evenly coated and loaded on paper by coating method, dipping method, spraying method or printing method. A layer of organic electrochromic material, but preferably requires coating, spraying or printing on both sides of the paper.

The counter electrode layer, ie, the ion storage layer, can be doped with one or more of TiO ₂ , NiO, CeO ₂ , IrO, V ₂ O ₅ , and the like. It can be directly prepared on the bottom ITO conductive glass by vacuum coating, magnetron sputtering, sol-gel coating method and other methods.

The polymer solid or gel-type polyelectrolyte ion conductor layer used in the present invention can make H ⁺ , Li ^+, etc. transport between the electrochromic layer and the counter electrode layer, that is, the ion storage layer, that is, the implantation and extraction of ions occurs, so as to Realize the reversible color development-fading change of the electrochromic layer. For this reason, the polymer solid or gel-type polyelectrolyte ion conductor used in the present invention requires good ionic conductivity, usually above 1× ^10-4 S·cm ^-1 , preferably 1× ^10-3 S·cm ^-1 or more, and secondly, the ionic conductor is required to have certain viscoelasticity, film-forming property and colorless transparency. It can be PEO derivatives-LiClO ₄ , PEU derivatives-LiClO ₄ , PPG-PMMA-LiClO ₄ , and blends and copolymers of PEO, PPG, PMMA, etc. and other organic materials, adding plasticizer and LiClO as the basic material ₄ The prepared polymer solid or gel polyelectrolyte ion conductor layer.

The preparation method of the above-mentioned device is as follows: firstly, the selected paper needs to be cut into a size that matches the ITO conductive glass substrate, used directly or printed with ink or printing ink containing adhesive, and after drying, use an inorganic Or the organic electrochromic material is uniformly coated on the untreated paper or in each cell on the treated paper to obtain the paper-supported electrochromic layer. Then on the conductive electrode layer on the top and the transparent glass base layer, that is, on the ITO conductive glass, make a polymer solid or gel-type polyelectrolyte ion conductor layer, and press it tightly; Make a polymer solid or gel polyelectrolyte ion conductor layer on the ITO conductive glass, and press it tightly; then place the paper-loaded electrochromic layer in the middle of the two ion conductor layers, and press it tightly; finally, the sides of each layer obtained Seal the package and connect the electrodes.

In addition, an organic or inorganic counter electrode layer, that is, an ion storage layer, can also be made between the conductive electrode layer at the bottom and the transparent glass substrate layer, that is, the ITO conductive glass, and the polymer solid or gel polyelectrolyte ion conductor layer.

A reversible color display change can be realized by applying a DC driving voltage between the conductive electrode layers of the two ITO conductive glasses. Etch the conductive electrodes of the two ITO conductive glasses into strips respectively. When assembling the electrochromic device, pay attention to make the strip electrodes of the two ITO conductive glasses cross each other perpendicularly, and print them on the paper with ink or printing ink containing adhesive. During grid processing, the length and width of the small grid on the paper are the same as and matched with the length, width and distance of the strip electrodes of the two ITO conductive glasses. The reflective all-solid-state paper-mounted electrochromic device prepared in this way can realize reversible matrix addressing information display by applying reversible DC driving voltage at different positions between the two ITO conductive glass strip electrode series that cross each other vertically. Variety. By applying a reversible DC driving voltage at different positions between the two ITO conductive glass strip electrode series with a certain program, the reversible automatic changing dynamic information display can be realized.

The role of the paper carrier in the present invention is: (1), providing a flexible carrier for the electrochromic material; (2), providing a high-white reflective background for the entire device; (3), providing partitions for the addressing and fixed-point display of the device ; (4), after the paper grid processing, it will provide pixel partition and isolation for the device, so that it can overcome defects such as "crosstalk phenomenon", "pixel discrete", pixel leakage, and image blur; (5), it can make the reflective type produced The all-solid-state paper-mounted electrochromic device plays the role and effect of double-sided synchronous display; (6), it provides the possibility of combining modern technologies such as screen printing, gravure printing, letterpress printing, and offset printing for the production and processing of the device; thus obtaining Low-cost electrochromic displays, electrochromic electronic ink, and electronic paper provide the possibility to achieve large-scale commercialization and popularization as soon as possible, and truly enter thousands of households.

Therefore, the reflective all-solid-state paper-mounted electrochromic device proposed by the present invention can not only greatly improve the contrast of the reflective all-solid-state paper-mounted electrochromic device as a display device, but also adopt pixel partition isolation technology on the paper carrier and the electrode simultaneously, It can further overcome the "crosstalk phenomenon", "pixel discrete", pixel leakage, image blurring and other problems, and combined with the existing screen printing, gravure printing, letterpress printing, offset printing and other technologies, it can realize automatic processing, so it is possible Get an inexpensive electrochromic display. It provides a new idea for the commercialization and popularization of electrochromic electronic ink and electronic paper, and lays a solid foundation for color electrochromic displays. In addition, the so-called electronic paper, digital paper or paper display in the past has no physical connection with paper, nor does it have the look and feel of paper. The reflective all-solid-state paper-mounted electrochromic device proposed by the present invention uses paper as a carrier for information display, and also has the appearance and texture of modern paper.

The invention lays the foundation for the full-color display and flexibility of the reflective all-solid-state paper-mounted electrochromic device, and lays the foundation for reducing the cost and price of electronic ink, electronic paper, digital paper or paper displays to a level that can be widely accepted by ordinary families .

Description of drawings:

Fig. 1 is a structural schematic diagram of the present invention.

Detailed ways

The implementation of the present invention will be further described below in conjunction with specific embodiments and accompanying drawings.

Example 1:

Viologen derivatives 1-ethyl-1'-(4-(4'-vinyl)benzyl)-4,4'-bipyridyl iodide chloride quaternary with styrene, acrylic acid, butyl acrylate Copolymer, ethanol, polyvinylpyrrolidone (PVP) are formulated into a suspension, evenly coated on both sides of ordinary white paper cut to match the size of the ITO conductive glass substrate, and baked under vacuum to remove the solvent to obtain Paper-borne electrochromic layer d. Place the prepared PEO derivative-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer c on the electrode side of a piece of ITO conductive glass ab. On the electrode side of another piece of ITO conductive glass gh, the NiO ion storage layer f is made by magnetron sputtering, and then the PEO derivative-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer e is placed. Place the paper-supported electrochromic layer d between the two ion conductor layers c and e, and press them tightly. Finally, the side surface of the obtained (abcdefgh) layer is sealed and packaged with a sealant i and connected with an external electrode. Two dry batteries were connected between the external electrodes, and the reflective all-solid-state paper-mounted electrochromic device shown in Figure 1 was fabricated. The paper-mounted electrochromic device displays a blue color when a voltage of 2.2-2.6V is applied, and the blue color can turn back to white when the reverse voltage is applied ^. Above, the open-circuit delay memory after color development can reach several days.

Example 2:

The viologen polycondensate, acetonitrile, and polyvinylpyrrolidone (PVP) prepared by condensation of viologen derivative 4,4′-bipyridine and chloroethyl chloroacetate was prepared into a suspension, and evenly coated on the cut-out and ITO The two sides of the ordinary white paper whose size is matched to the conductive glass substrate are baked under vacuum to remove the solvent, forming the paper-borne electrochromic layer d. Place the prepared PEU derivative-LiClO ₄ gel polyelectrolyte ion conductor layer c on the electrode side of a piece of ITO conductive glass ab. On the electrode side of another piece of ITO conductive glass gh, the TiO ₂ ion storage layer f is made by sol-gel spin coating method, and then the PEU derivative-LiClO ₄ gel-type polyelectrolyte ion conductor layer e is placed. Place the paper-supported electrochromic layer d between the two ion conductor layers c and e, and press them tightly. Finally, the side surface of the obtained (abcdefgh) layer is sealed and packaged with a sealant i and connected with an external electrode. Two dry batteries were connected between the external electrodes, and the reflective all-solid-state paper-mounted electrochromic device shown in Figure 1 was fabricated. The discoloration performance, number of color development cycles, and open-circuit delay memory performance of the paper-mounted electrochromic device are similar to those of Example 1.

Example 3:

Viologen derivative bromide 1-phosphonic acid ethyl 1′-ethyl-4,4′-bipyridyl, acetonitrile, polyvinylpyrrolidone (PVP) prepared into a suspension, evenly coated on the cut into The two sides of ordinary white paper matching the size of the ITO conductive glass substrate are baked under vacuum to remove the solvent, forming the paper-borne electrochromic layer d. Place the prepared epichlorohydrin-dichloromethane-PEO-LiClO ₄ gel-type polyelectrolyte ion conductor layer c in the presence of KOH on the electrode side of a piece of ITO conductive glass ab. On the electrode side of another piece of ITO conductive glass gh, the polyaniline ion storage layer f made by electropolymerization is placed, and the -PEO-LiClO ₄ gel polyelectrolyte treated with epichlorohydrin-dichloromethane in the presence of KOH is placed. Ionic conductor layer e. Place the paper-supported electrochromic layer d between the two ion conductor layers c and e, and press them tightly. Finally, the side surface of the obtained (abcdefgh) layer is sealed and packaged with a sealant i and connected with an external electrode. Two dry batteries were connected between the external electrodes, and the reflective all-solid-state paper-mounted electrochromic device shown in Figure 1 was fabricated. The paper-mounted electrochromic device's color changing performance, color cycle times, open-circuit delay memory performance and

Example 1 is close.

Example 4:

Nano-WO ₃ powder doped with 5% TiO ₂ , 6% MoO ₃ , H ₂ O ₂ , solvent-diluted styrene-acrylic acid-butyl acrylate copolymer adhesive and other additives are prepared into a suspension, and evenly coated on both sides On ordinary white paper cut to match the size of the ITO conductive glass substrate, the solvent is baked under vacuum to form the paper-borne electrochromic layer d. Two pieces of ITO conductive glass ab, gh are respectively placed the prepared PEO-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layers c and e, and the paper electrochromic layer d is placed on the two ion conductor layers c and e Between, tightly pressed. Finally, the side surface of the obtained (abcdegh) layer is sealed and packaged with a sealant i and connected with an external electrode wire. Three dry batteries were connected between the external electrode wires, and the reflective all-solid-state paper-mounted electrochromic device shown in Figure 1 was fabricated. When a voltage of 3.5-4V is applied, the device displays a dark blue color. When the voltage is applied in the opposite direction, the dark ^blue color can turn back to white. The open-circuit delay memory can reach several days.

Example 5:

Use styrene, acrylic acid, butyl acrylate copolymerized adhesive diluted with appropriate solvent to align and print 16×16 small grids on both sides of ordinary white paper, each small grid area is 3.5mm×3.5mm, adhesive printing The line width is 0.5 mm, and the solvent is vacuum dried. Nanometer WO ₃ powder doped with 8% MoO ₃ , H ₂ O ₂ , solvent-diluted styrene-acrylic acid-butyl acrylate copolymer adhesive, and prepared as a suspension, uniformly coated on both sides or printed on each of the above papers In a small grid, the solvent is baked under vacuum to remove the solvent, which is the paper-borne electrochromic layer d.

Two pieces of 80mm×90mm ITO conductive glass were etched on the ITO conductive layer with etching technology to carve 16 strip-shaped electrodes with a width of 3.5mm and a length of 82mm, and the etching line width was 0.5mm. The strip electrodes are etched on three sides to make them non-conductive. Place the prepared PEO-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer c on one side of the strip-shaped electrode of a piece of ITO conductive glass ab. On the strip electrode side of another piece of ITO conductive glass gh, the Prussian blue ion storage layer f was fabricated by sol-gel spin coating method, and then the PEO-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer e was placed. Place the paper-supported electrochromic layer d between the two ion conductor layers c and e, make the strip electrodes of abc and efgh perpendicular to each other, and make the small grid on d also align with the two strip electrodes, and press them tightly. Finally, the side surfaces of the obtained (abcdefgh) layer were sealed and packaged with a sealant, and 32 external electrode wires were connected and drawn out. Connect 3 dry batteries between the external electrode wires, and the reflective all-solid-state paper-mounted electrochromic device shown in Figure 1 can be made. When a voltage of 3.5-4V is applied, the pixels display a dark blue color, and when the voltage is reversely applied, the dark ^blue color can turn back to white. The last open-circuit delay memory can reach several days. The paper-mounted electrochromic device has 16×16=256 pixels, which can realize matrix addressing and fixed-point display, and can also realize multi-point display and simple symbol information display.

Example 6

Styrene, acrylic acid, butyl acrylate copolymerized adhesive diluted with appropriate solvents, align and print 64×64 small grids on both sides of ordinary white paper, each small grid area is 1.6mm×1.6mm, adhesive printing The line width is 0.4 mm, and the solvent is vacuum dried. The suspension prepared from methyl viologen polymer, polyvinylpyrrolidone (PVP), styrene-acrylic acid-butyl acrylate terpolymer and other additives was used as red EC material. The suspension prepared by polyaniline doped with acrylic acid-propylene sulfonic acid copolymer, water, ethanol and other additives was used as green EC material. Tetrapolymer of 1-ethyl-1′-propenyl-4,4′-bipyridyl bromide iodide with viologen derivatives, styrene, acrylic acid, butyl acrylate, ethanol, polyvinylpyrrolidone (PVP) was formulated as a suspension as a blue EC material. Coating or printing red EC material according to lines 1, 4, 7, 10, 13...64, etc., coating or printing blue EC material according to lines 2, 5, 8, 11, 14...62, etc. Coat or print green EC materials in 3, 6, 9, 12, 15...63 lines, etc., evenly coat or print the three EC materials in each small grid on the above paper, and both sides must be aligned cloth or printing. The solvent is baked under vacuum to obtain the paper-supported electrochromic layer d.

Two pieces of 152mm×165mm ITO conductive glass were etched on the ITO conductive layer with etching technology to carve 64 strip-shaped electrodes with a width of 1.6mm and a length of 154mm, and the etching line width was 0.4mm. The strip electrodes are etched on three sides to make them non-conductive. Place the prepared PPG-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer c on one side of the strip electrode of a piece of ITO conductive glass ab. PPG-PMMA-LiClO ₄ gel-type polyelectrolyte ion conductor layer e is placed on the strip electrode side of another piece of ITO conductive glass gh. Place the paper-supported electrochromic layer d between the two ion conductor layers c and e, make the strip electrodes of abc and egh perpendicular to each other, and make the small grid on d also align with the two strip electrodes, and press them tightly. Finally, the side surfaces of the obtained (abcdegh) layer were sealed and packaged with sealant i, and 128 external electrode wires were connected and drawn out. Two dry batteries were connected between the external electrode wires, and the color reflective all-solid-state paper-borne electrochromic device shown in Figure 1 was made. The paper-mounted electrochromic device has 64×64=4096 pixels. When a voltage of 2.0-2.5V is applied, the red, blue, and green pixels display red, blue, and green respectively; when the reverse voltage is applied, the three colors can be displayed. Turning back to white, the color change response time is 20-100 seconds, the number of color development cycles can reach more than 4×10 ⁶ , and the open circuit delay memory after color development can reach several days. If a reversible DC driving voltage is applied to the 128 external electrode lines with a certain program, the reversible automatic changing dynamic information display color pattern can be realized.

Claims (10)

1. A reflective all-solid-state paper-borne electrochromic device made of paper-borne organic or inorganic electrochromic materials, characterized in that the paper-borne electrochromic layer (d) is used as the The main display film, the two sides of the paper-borne electrochromic layer (d) are tightly pressed with the ion conductor layers (c, e) made of polymer solid or gel polyelectrolyte, and the ion conductor layer (c) on one side is There is a conductive electrode layer (b) and a transparent glass base layer (a), and the ion conductor layer (e) on the other side also has a conductive electrode layer (g) and a transparent glass base layer (h), and the sides of the above layers are sealed together The electrodes are encapsulated and connected. 2. The reflective all-solid-state paper-mounted electrochromic device according to claim 1, characterized in that: there are organic Or the inorganic counter electrode layer, ie the ion storage layer (f). 3. The reflective all-solid-state paper-borne electrochromic device according to claim 1 or 2, characterized in that: conductive electrode layer (b) and transparent glass base layer (a) and conductive electrode layer (g) and transparent glass The base layer (h) can directly use commercially available ITO conductive glass. 4. The reflective all-solid-state paper-mounted electrochromic device according to claim 1 or 2, characterized in that: the paper-mounted electrochromic layer (d) is made of paper as the carrier of the electrochromic material, coated with The solution or suspension of the electrochromic material is evenly coated and loaded on the paper by cloth method, dipping method, spraying method or printing method, and is obtained after vacuum drying to remove the solvent. 5. The reflective all-solid-state paper-mounted electrochromic device according to claim 4, characterized in that: the paper used as the carrier of the organic electrochromic material is a commercially available variety of types and grades of white mechanism or handmade printing. paper, copy paper, writing paper or calligraphy paper. 6. The reflective all-solid-state paper-mounted electrochromic device according to claim 4, characterized in that: the paper used as the carrier of the electrochromic material is used directly or printed small The grid is used after partitioning and grid processing. 7. The reflective all-solid-state electrochromic device on paper according to claim 4, characterized in that the electrochromic material loaded on the paper is inorganic electrochromic materials WO ₃ , MoO ₃ , TiO ₂ , Nb ₂ Doped with one or more of O ₅ and V ₂ O ₅ ; or dispersed in an organic solvent or an aqueous solution containing an organic solvent by using one or more of the doped ultrafine powder or nanopowder Suspension dip coating material. 8. The reflective all-solid-state paper-mounted electrochromic device according to claim 4, characterized in that: the organic electrochromic material loaded on the paper is viologen, that is, various derivatives of 4,4'-bipyridine or various derivatives, polymers or copolymers of metal phthalocyanines; or derivatives or copolymers of polyaniline; or derivatives or copolymers of polythiophene; or Derivatives or copolymers of polypyrrole; or polymeric metal complexes or Prussian blue containing organic ligands. 9. The reflective all-solid-state paper-mounted electrochromic device according to claim 1, its preparation method comprising the following process steps: (1) Cut the paper into a size that matches the ITO conductive glass substrate, use it directly or use it after printing with ink or printing ink containing adhesive; (2) Evenly coating the organic electrochromic material on the paper used directly or in each small grid on the paper after grid treatment, to obtain the paper-borne electrochromic layer (d); (3) Place the ionic conductor layer (c) made of polymer solid or gel polyelectrolyte on the top ITO conductive glass (ab) and tightly press it; (4) Make another ion conductor layer (e) on the bottom ITO conductive glass or (gh); (5) The paper-supported electrochromic layer (d) is placed between the ion conductor layers (c) and (e) and pressed tightly, so that the abcdegh layer is integrated; (6) Finally, the side surface of the obtained (abcdegh) layer is sealed and sealed and connected with electrodes. 10. The preparation method of reflective all-solid-state paper-mounted electrochromic device according to claim 9, characterized in that an organic or The inorganic counter electrode layer is the ion storage layer (f); the ion storage layer (f) is the inorganic electrochromic counter electrode film TiO ₂ or NiO, or various derivatives of organic electrochromic counter electrode film metal phthalocyanine, Polymers or copolymers, or derivatives or copolymers of polyaniline, or derivatives or copolymers of polythiophene, or derivatives or copolymers of polypyrrole, using magnetron sputtering on the bottom ITO conductive glass (gh) , electrochemical deposition or sol-gel coating method.