CN104407483A - Electrochromic device and preparation method and application thereof - Google Patents

Abstract

The invention discloses an electrochromic device and its preparation method and application. A first conductive layer is deposited on the surface of a first substrate by a coating process; a first electrochromic layer is deposited on a mask on the surface of the first conductive layer; The process sequentially deposits an electrolyte layer and a second conductive layer on the surface of the first electrochromic layer; or prepares an electrolyte layer between the second conductive layer and the first electrochromic layer after depositing the second conductive layer on the surface of the second substrate ; Obtain a single-layer electrochromic device; or, adopt a coating process to sequentially deposit an electrolyte layer, a second electrochromic layer and a second conductive layer on the surface of the first electrochromic layer; or deposit the second electrochromic layer sequentially on the surface of the second substrate After the conductive layer and the second electrochromic layer, an electrolyte layer is prepared between the second electrochromic layer and the first electrochromic layer; a double-layer electrochromic device is obtained; the electrolyte layer is a transparent solid organic lithium ion conductor film. Its all-solid-state preparation process effectively solves the problem that it is difficult to achieve large-scale large-scale production.

Description

Electrochromic device and its preparation method and application

technical field

The invention relates to the field of electronic devices, in particular to an electrochromic device and its preparation method and application.

Background technique

Electrochromism refers to the phenomenon that the optical properties of materials (reflectivity, transmittance, absorptivity, etc.) undergo a stable and reversible color change under the action of an external electric field, which is manifested as a reversible change in color and transparency in appearance. Materials with electrochromic properties are called electrochromic materials. Therefore, the electrochromic material has a bistable performance. The electrochromic display device made of the electrochromic material not only does not need a backlight, but after displaying a static image, as long as the content of the displayed image remains unchanged, it will not consume electricity. electricity. Therefore, it has a good energy-saving effect. Moreover, compared with other display devices, electrochromic display devices have the advantages of no visual blind angle, high contrast, wide operating temperature range, low driving voltage and rich colors. Great application prospects.

Among the electrochromic transition metal oxides, vanadium pentoxide exhibits both anodic and cathodic discoloration, and molybdenum-doped vanadium pentoxide films have polyelectrochromic (orange-yellow-green-blue) behaviour, 30%-90% optical modulation in the 550nm-900nm spectral region. Therefore, using molybdenum-doped vanadium pentoxide as the electrochromic layer in the electrochromic device can effectively improve the performance of the electrochromic device. However, in the preparation of electrochromic devices, it is difficult to achieve large-scale production due to the high cost of raw materials and production costs, and the performance of the prepared electrochromic devices is not stable enough.

Contents of the invention

Based on this, it is necessary to provide an electrochromic device and its preparation method and application in view of the problems that the existing electrochromic device has high manufacturing cost and it is difficult to realize large-scale production.

A kind of preparation method of electrochromic device provided for realizing the purpose of the present invention, comprises the following steps:

Depositing a first conductive layer on the surface of the first substrate by a coating process;

Depositing a first electrochromic layer with a mask on the surface of the first conductive layer;

The electrolyte layer and the second conductive layer are sequentially deposited on the surface of the first electrochromic layer by the coating process; or after the second conductive layer is deposited on the surface of the second substrate, the second conductive layer and the second conductive layer are deposited on the surface of the second substrate Prepare the electrolyte layer between the first electrochromic layer; obtain a single-layer electrochromic device;

Or, using the coating process to sequentially deposit the electrolyte layer, the second electrochromic layer and the second conductive layer on the surface of the first electrochromic layer; or sequentially deposit the electrochromic layer on the surface of the second substrate. After the second conductive layer and the second electrochromic layer, the electrolyte layer is prepared between the second electrochromic layer and the first electrochromic layer; a double-layer electrochromic device is obtained;

The electrolyte layer is a transparent solid organic lithium ion conductor film.

In one of the embodiments, preparing the electrolyte layer includes:

After injecting or injecting electrolyte sol between the second conductive layer and the first electrochromic layer, or between the second electrochromic layer and the first electrochromic layer, after preset Baking at a baking temperature until the electrolyte sol is polymerized and solidified to form the transparent solid organic lithium ion conductor film;

Wherein, the electrolyte sol is an organic lithium ion sol.

In one embodiment, the preset baking temperature is 50°C-200°C.

In one embodiment, the deposition processes of the first electrochromic layer and the second electrochromic layer are both electrochemical deposition processes or magnetron sputtering deposition processes.

Correspondingly, the present invention also provides an electrochromic device prepared by any one of the above preparation methods, including a conductive layer, an electrochromic layer and an electrolyte layer;

Wherein, the electrolyte layer is a transparent solid organic lithium ion conductor film.

In one of the embodiments, the transmittance of the transparent solid organic lithium ion conductor film in the visible light range is greater than or equal to 80%; and,

The thickness of the transparent solid organic lithium ion conductor film is 50nm-5mm.

In one embodiment, the ionic conductivity of the transparent solid organic lithium ion conductor film is greater than or equal to 1×10 ^-5 S/cm.

In one of the embodiments, the electrochromic layer is a molybdenum-doped vanadium pentoxide thin film; and,

The molybdenum-doped vanadium pentoxide thin film has a [001]-oriented layered structure.

In one of the embodiments, in the molybdenum-doped vanadium pentoxide thin film, the doping concentration of molybdenum is 5%-10%mol; and,

The molybdenum-doped vanadium pentoxide thin film has a thickness of 50 nm to 5 μm.

Correspondingly, the present invention also provides an application of any one of the above-mentioned electrochromic devices on a mobile terminal.

Beneficial effects of the above electrochromic device preparation method:

The preparation of an all-solid-state electrochromic device is achieved by preparing a transparent solid-state organic lithium ion conductor film as an electrolyte layer in a single-layer electrochromic device or a double-layer electrochromic device. The preparation process is simple, low in cost and easy to realize, and the all-solid-state preparation process (that is, the conductive layer, the electrochromic layer and the electrolyte layer are all solid) is conducive to large-scale production. Therefore, the problems that the existing electrochromic devices are relatively high in production cost and difficult to achieve large-scale production are effectively solved.

Moreover, the electrochromic device prepared by the above method is an all-solid-state electrochromic device, and the all-solid-state electrochromic device has higher performance stability than the solid-liquid coexisting electrochromic device. Therefore, the performance stability of the electrochromic device is effectively improved.

Description of drawings

Fig. 1 is the structural sectional view of a specific embodiment of the electrochromic device of the present invention;

Fig. 2 is a structural sectional view of another specific embodiment of the electrochromic device of the present invention;

Fig. 3 is the XRD spectrum of the molybdenum-doped vanadium pentoxide electrochromic thin film prepared by the embodiment 1 of the electrochromic device preparation method of the present invention;

Fig. 4 is a graph of the transmittance data of the electrochromic device prepared by using Example 1 of the preparation method of the electrochromic device of the present invention.

Detailed ways

In order to make the technical solution of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific embodiments.

As a specific embodiment of the preparation method of the electrochromic device provided by the present invention, it includes the following steps:

Step S100, depositing a first conductive layer on the surface of the first substrate by using a coating process.

Step S200, depositing a first electrochromic layer on the surface of the first conductive layer with a mask.

In step S300, an electrolyte layer and a second conductive layer are sequentially deposited on the surface of the first electrochromic layer by using a coating process. That is, after the electrolyte layer is deposited on the surface of the first electrochromic layer, the second conductive layer is deposited on the surface of the electrolyte layer. The preparation of the single-layer electrochromic device can be completed. Alternatively, after depositing the second conductive layer on the surface of the second substrate, the second conductive layer and the first electrochromic layer are packaged, and an electrolyte layer is directly prepared between the second conductive layer and the first electrochromic layer to achieve Fabrication of monolayer electrochromic devices.

Alternatively, in step S300', the electrolyte layer, the second electrochromic layer and the second conductive layer are sequentially deposited on the surface of the first electrochromic layer by a coating process, so as to realize the preparation of a double-layer electrochromic device. Or after depositing the second conductive layer and the second electrochromic layer sequentially on the surface of the second substrate, an electrolyte layer is prepared between the second electrochromic layer and the first electrochromic layer to achieve the preparation of a double-layer electrochromic device the goal of.

Wherein, the electrolyte layer in the single-layer electrochromic device or the double-layer electrochromic device prepared above is a transparent solid organic lithium (Li) ion conductor film.

The electrochromic device prepared by the above preparation method is composed of a multilayer composite film, and has the most typical and simplest structure of the electrochromic device. And by preparing a transparent solid organic Li ion conductor film as a solid electrolyte layer, an all-solid-state electrochromic device is realized, and the performance of the device is more stable. Moreover, the preparation process is simple, and it is easy to realize large-scale large-scale production.

As a specific example, when preparing the electrolyte layer, the electrolyte sol can be injected or injected between the first electrochromic layer and the first conductive layer, or between the first electrochromic layer and the first electrochromic layer by using the injection method or vacuum infusion method. The second electrochromic layer is baked at a preset baking temperature until the electrolyte sol is polymerized and solidified to form a transparent solid organic lithium ion conductor film. Wherein, the electrolyte sol is organic lithium ion sol.

The organic lithium ion sol is used to form a solid electrolyte layer, and the manufacturing process is simple and the cost is low. Wherein, the preset temperature is preferably 50°C-200°C.

Referring to FIG. 1 , it is illustrated in detail with the prepared single-layer electrochromic device.

Firstly, the first conductive layer 120 is deposited on the surface of the first substrate 110 through a coating process. The first conductive layer 120 is used as a cathode electrode of the electrochromic device, therefore, the first conductive layer 120 can also be called a cathode conductive layer. The first substrate 110 can be made of transparent glass, which is easy to obtain and low in cost. Meanwhile, the first conductive layer 120 is preferably a transparent conductive layer. Specifically, it can be realized by depositing a metal oxide film. Wherein, the metal oxide film may be: indium tin oxide (ITO) film, indium zinc oxide (IZO) film, indium gallium zinc (IGZO) film, or aluminum zinc oxide (AZO) film.

Then, the first electrochromic layer 130 is deposited on the surface of the first conductive layer 120 through a mask. The mask mentioned here means that any corner of the first conductive layer 120 is covered by a mask plate or a cover plate having a covering function as an electrode contact area. Then the first electrochromic layer 130 is deposited on the surface of the uncovered part of the first conductive layer 120 . The deposition process of the first electrochromic layer 130 can be realized by an electrochemical deposition process or a magnetron sputtering deposition process. Of course, other physical vapor deposition processes or chemical vapor deposition processes can also be used. It is preferably an electrochemical deposition process or a magnetron sputtering deposition process, which can be deposited at room temperature, with simpler operation, lower process cost, easy large-scale growth, and better compatibility with existing electronic device processes , which is more conducive to the realization of large-scale large-scale production.

It should be pointed out that the structure of the first electrochromic layer 130 is a layered structure. By adjusting the deposition process parameters of the first electrochromic layer 130 , the structure of the first electrochromic layer 130 is made into a layered structure, which is more conducive to the passage of lithium ions in the electrolyte layer 140 . The layered structure of the first electrochromic layer 130 enables lithium ions in the electrolyte layer 140 to have a higher degree of freedom and better ion transport performance, thereby improving the adsorption-desorption and transfer of lithium ions, making the first electrochromic The reversible color change of the color-changing layer 130 is more stable. Finally, the performance and stability of electrochromic devices are improved.

After the first electrochromic layer 130 is deposited on the surface of the first conductive layer 120 , the electrolyte layer 140 can be prepared. As mentioned above, the preparation of the electrolyte layer 140 can be achieved in two ways. First, the electrolyte layer 140 is directly deposited on the surface of the first electrochromic layer 130 by using a coating process; second, it is prepared by an injection method or a vacuum infusion method.

The following takes the preparation of the electrolyte layer 140 by the injection method as an example for specific description.

When the injection method is adopted, the electrolyte sol needs to be injected between the first electrochromic layer 130 and the second conductive layer 150 (ie, the anode conductive layer). Therefore, it is first necessary to prepare the second conductive layer 150 . The preparation process of the second conductive layer 150 can be directly deposited on the surface of the second substrate 160 by a coating process. Wherein, the second substrate 160 can also choose transparent glass; the second conductive layer 150 is also preferably a transparent conductive layer, which can be realized by depositing a metal oxide film.

After the second conductive layer 150 is deposited on the surface of the second substrate 160, the second conductive layer 150 and the first electrochromic layer 130 are packaged with an encapsulation material (which may be epoxy resin). Then, the electrolyte sol is directly injected between the second conductive layer 150 and the first electrochromic layer 130 using a syringe. Since the electrolyte layer in the electrochromic device of the present invention is a transparent solid organic lithium ion conductor film, the injected electrolyte sol is preferably an organic lithium ion sol.

After the organic lithium ion sol is injected between the second conductive layer 150 and the first electrochromic layer 130, the organic lithium ion sol injected between the second conductive layer 150 and the electrochromic layer 130 is heated in a preset oven. Bake at roasting temperature. Until the organic lithium ion sol is polymerized and solidified to form a transparent solid organic lithium ion conductor film.

It should be noted that when the organic lithium ion sol is baked in an atmosphere with a vacuum degree of 1Pa-1000Pa, the baking temperature is inversely proportional to the baking time. The higher the baking temperature, the shorter the baking time. Conversely, the lower the baking temperature, the longer the baking temperature. In addition, when the organic lithium ion sol is baked, it may be directly carried out under an air atmosphere. Simple operation and easy implementation. Conducive to large-scale production.

In addition, a transparent solid organic lithium ion conductor film is used as the electrolyte layer 140, and its transmittance in the visible light range is greater than or equal to 80%. Also, the thickness of the transparent solid organic lithium ion conductor film is preferably 50 nm (nanometer) to 5 mm (millimeter).

Further, the first electrochromic layer 130 is preferably a molybdenum-doped vanadium pentoxide film. Molybdenum-doped vanadium pentoxide film is used as the first electrochromic layer 130 of the electrochromic device, when +3.0V, +1.0V, -1.0V and -3.0V are applied to the cathode electrode and the anode electrode of the electrochromic device When V is pressed squarely, the electrochromic device can be reversibly changed between orange-yellow-green-blue.

Meanwhile, preferably, the molybdenum-doped vanadium pentoxide film deposited on the surface of the first conductive layer 120 has a [001]-oriented layered structure. That is to say, the molybdenum-doped vanadium pentoxide thin film deposited on the first conductive layer 120 preferentially grows along the [001] crystal direction.

It should be noted that, in the molybdenum-doped vanadium pentoxide thin film, the doping concentration of molybdenum is 5%˜10%mol.

Moreover, the color of the electrochromic device is related to the thickness of the first electrochromic layer 130 . Under the same step voltage, the thicker the electrochromic layer 130 is, the darker the color will be. When the molybdenum-doped vanadium pentoxide film reaches a certain thickness, the color of the electrochromic device can be orange-yellow-(yellow) under the square voltage driving of +3.0V, +1.0V, -1.0V and -3.0V. -green)-(green-blue), not just orange-yellow-green-blue. This also increases the color change of the electrochromic device. Therefore, the thickness of the molybdenum-doped vanadium pentoxide thin film can be 50nm (nanometer) to 5 μm (micrometer).

Through power management and circuit integration, the electrochromic device is integrated on the back shell of electronic terminal equipment, such as mobile phones, tablet computers, etc., to meet the personalized color needs of consumers.

Furthermore, the coating process can be a physical vapor deposition process or a chemical vapor deposition process. When preparing the electrochromic device of the present invention, the coating process can be selected according to the actual situation, which increases the flexibility and compatibility of the process. Also, a magnetron sputtering deposition process is preferred. In the magnetron sputtering deposition process, atoms are sputtered out after exchanging energy with high-energy ions, and their energy is 1-2 orders of magnitude higher than that of evaporated atoms. Thus, the conductive layer (i.e. the first conductive layer 120 and the second conductive layer 150) and the substrate (i.e. the first substrate 110 and the second substrate 160) in the electrochromic device prepared by the magnetron sputtering deposition process ) have better adhesion.

It should be understood that the preparation of the first electrochromic layer 130 and the conductive layer is not limited to the aforementioned electrochemical deposition process and magnetron sputtering deposition process. It also includes vacuum thermal evaporation deposition process, enhanced chemical vapor deposition process (PECVD), sol-gel deposition process or spray deposition process, etc.

Referring to FIG. 2 , as a specific embodiment of a double-layer electrochromic device, a second electrochromic layer 180 is added to the electrolyte layer 140 and the second conductive layer 150 . Wherein, the preparation of the second electrochromic layer 180 is the same as or similar to that of the first electrochromic layer 130 , so details are not repeated here. Likewise, the second electrochromic layer 180 is preferably a layered structure.

Moreover, the materials of the second electrochromic layer 180 and the first electrochromic layer 130 may be the same or different. Different preparations can be carried out according to specific situations.

In summary, the electrochromic device of the present invention prepared by the above steps is a single-layer electrochromic device or a double-layer electrochromic device, which is composed of a multi-layer all-solid composite film. Wherein, the electrolyte layer 140 is a transparent solid organic lithium ion conductor film. Simple structure and more stable performance. Moreover, except for the electrochromic layer 130 , the transmittances of the other film layers in the visible light range are all above 80%, which effectively improves the performance of the electrochromic device.

More specifically, the present invention will be further described with specific examples below.

Example 1

Referring to FIG. 1 , in the single-layer multi-color electrochromic device provided in Embodiment 1, the first substrate 110 is an ordinary transparent glass sheet. The first conductive layer 120 is an indium tin oxide (ITO) film, which is used to communicate with an external power source and serves as a cathode electrode. The first electrochromic layer 130 is a molybdenum-doped vanadium pentoxide film. The electrolyte layer 140 is a polymer lithium salt solid electrolyte membrane. The second substrate 160 is an ordinary transparent glass sheet. The second conductive layer 150 is an ITO film, which is used to communicate with an external power source and serves as an anode electrode. Use epoxy resin 170 to laminate and seal the two coated transparent glass sheets.

The preparation method of the above-mentioned single-layer electrochromic device comprises the following steps:

Firstly, ordinary transparent glass with an area of 2.5×2.5 cm ² cleaned by ultrasonic cleaning with acetone and absolute ethanol solution is used as the first substrate 110. The transmittance of the ordinary glass in the visible light range is over 80%, and the surface is smooth. And has a planar structure.

Then, a layer of ITO thin film with a thickness of 50 nm-5 μm is deposited on the first substrate 110 by magnetron sputtering method as the first conductive layer 120 .

Secondly, a mask plate is used to cover one corner of the ITO film as an electrode contact area, and a molybdenum-doped vanadium pentoxide film with a thickness of 800 nm is deposited on the ITO film by electrodeposition as the first electrochromic layer. 130.

Next, an ITO thin film with a thickness of 50 nm˜5 μm is deposited on the second substrate 160 by magnetron sputtering as the second conductive layer 150 . A mask plate or other covering plates with the same covering function are used to cover a corner of the ITO film (here referred to as the second conductive layer 150 ) as an electrode contact area.

Then, use screen printing to pattern epoxy resin glue on the edge of the V ₂ O ₅ :Mo/ITO and ITO film to form a multi-color all-solid-state electrochromic device cell with a reserved small hole. The V ₂ O ₅ : Mo/ITO diaphragm and the edge of the ITO diaphragm are glued together with epoxy resin cured at 130°C-140°C to assemble a diaphragm cavity for subsequent filling of Li ⁺ ionic liquid electrolyte . The height of the diaphragm cavity is generally 30 μm to 200 μm (controlled by the spherical glass bead height limiter in the epoxy resin glue). This diaphragm cavity is called "cell void" in the liquid crystal industry. Then, the vacuum infusion method and the "dropping-pressure" method are used to inject the Li ⁺ ionic liquid electrolyte material into the membrane cavity, that is, between the V ₂ O ₅ :Mo/ITO membrane and the ITO membrane.

Specifically, before vacuum infusion, the membrane cavity and Li ⁺ ionic liquid electrolyte are pre-evacuated to eliminate the residual gas that is easily volatilized under low pressure. Firstly, the cavity of the diaphragm is clamped on the base, and the reserved small hole is placed above the liquid electrolyte container and its position can be adjusted at will. Subsequently, the filling chamber is closed and evacuated with a mechanical pump. When the gas pressure drops to about 10 Pa, the base is rotated and the multi-color all-solid-state electrochromic device is lowered so that the liquid electrolyte is immersed in the reserved small hole. Due to the principle of liquid capillarity, the Li ⁺ ionic liquid electrolyte flows into the diaphragm cavity due to the open gas inlet. Turn off the vacuum pump and maintain low pressure for a certain period of time (about 5min). When the air inlet is slowly opened, the internal air pressure will rise slowly. This creates a pressure differential between the atmospheric pressure on the liquid surface and the vacuum inside the membrane cavity, which facilitates the flow of the Li ⁺ ionic liquid electrolyte into the membrane cavity. When the Li ⁺ ionic liquid electrolyte in the membrane cavity is filled to about 80%, the air inlet of the chamber is fully opened so that the air pressure quickly returns to atmospheric pressure, and 100% of the liquid is filled. After priming is complete, rotate the base again and remove the gas inlet from the liquid electrolyte. The open part of the reserved hole is glued with UV resin and cured quickly. Finally, after baking at 85°C for 2 hours, the organic Li ⁺ ionic liquid electrolyte in the cavity of the diaphragm is cross-linked and solidified to form an organic lithium ion conductor film, which is used as the electrolyte layer 140 of the electrochromic device, thereby obtaining a monolayer Multi-color all-solid-state electrochromic devices.

Referring to FIG. 3 , it is an XRD pattern obtained by XRD (X-ray diffraction, X-ray diffraction) scanning of the molybdenum-doped vanadium pentoxide thin film prepared in Example 1. It can be clearly seen from the XRD spectrum that, in addition to the diffraction peak of the ITO film, there is only a strong diffraction peak of the [001] orientation of the vanadium pentoxide film, indicating that the molybdenum-doped vanadium pentoxide film (ie, the electrochromic layer 130) It grows preferentially along [001]. Under the molybdenum-doped vanadium pentoxide film structure preferentially grown along [001], lithium ions have a higher degree of freedom and good ion transport performance, which is conducive to the adsorption-desorption and transfer of ions, and can improve the electrochromic effect. device sensitivity.

Referring to FIG. 4 , it is a graph of transmittance data of the electrochromic device prepared in Example 1 above. It can be seen from the transmittance data graph that the optical transmittance of the electrochromic device can be effectively regulated by applying a voltage between the cathode electrode and the anode electrode.

In addition, by applying +3.0V, +1.0V, -1.0V and -3.0V square voltages between the cathode electrode and the anode electrode of the all-solid-state single-layer multi-color electrochromic device prepared in Example 1, it is obtained that The single-layer electrochromic device reversibly changes between orange-yellow-green-blue.

Example 2

Referring to FIG. 2 , it is a specific embodiment of a double-layer electrochromic device, and the first substrate 110 is an ordinary transparent glass sheet. The first conductive layer 120 is an indium tin oxide (ITO) film, which is used to communicate with an external power source and serves as a cathode electrode. The first electrochromic layer 130 is a molybdenum-doped vanadium pentoxide film. The electrolyte layer 140 is a polymer lithium salt solid electrolyte membrane. The second substrate 160 is an ordinary transparent glass sheet. The second conductive layer 150 is an indium tin oxide (ITO) film, which is used to communicate with an external power source and serves as an anode electrode. The second electrochromic layer 180 is a tungsten oxide (WO ₃ ) or nickel oxide (NiO) film. Use epoxy resin 170 to laminate and seal the two coated transparent glass sheets.

The manufacturing method of the above-mentioned double-layer electrochromic device comprises the following steps:

First, ordinary glass with an area of 2.5×2.5 cm ² cleaned by ultrasonic cleaning with acetone and absolute ethanol solution was used as the transparent first substrate 110 . The common glass has a transmittance of more than 80% in the range of visible light, and has a smooth surface and a planar structure.

Next, a layer of ITO thin film with a thickness of 50 nm-5 μm is deposited on the first substrate 110 by magnetron sputtering as the first conductive layer 120 , that is, the cathode conductive layer.

Then, use a mask plate or other covering plate to cover one corner of the ITO film as an electrode contact area, and deposit a molybdenum-doped vanadium pentoxide film with a thickness of 800nm on the ITO film by magnetron sputtering as the second electrode contact area. An electrochromic layer 130 .

Next, a layer of ITO thin film with a thickness of 50 nm-5 μm is also deposited on the second substrate 160 by magnetron sputtering as the second conductive layer 150 , that is, the anode conductive layer.

Then, a corner of the ITO film (here referred to as the second conductive layer 150) is covered by a mask plate or other covering plates with the same covering function as the electrode contact area, and the magnetron sputtering method is used on the ITO film ( It refers to depositing a layer of WO ₃ or NiO thin film on the second conductive layer 150) as the second electrochromic layer 180.

Next, use epoxy resin 170 to separate and seal the V ₂ O ₅ :Mo/ITO diaphragm and WO ₃ (NiO)/ITO diaphragm with a certain thickness of plexiglass frame, leaving small holes for electrolytic sol injection Entrance.

Finally, the two prepared membranes are placed in a vacuum chamber and baked at 100° C. to 300° C. to remove moisture. Then, the colorless and transparent organic lithium ion sol is injected between the two diaphragms by vacuum infusion, and baked at a preset baking temperature, so that the organic lithium ion sol is polymerized and completely cured to form an organic lithium ion conductor film , as the electrolyte layer 140 of the electrochromic device, a multi-layer all-solid-state multi-color electrochromic device is finally obtained.

By applying driving square voltages of +3.0V, +1.0V, -1.0V and -3.0V between the cathode electrode and the anode electrode of the all-solid-state multi-color electrochromic device prepared in Example 2, the multilayer electrochromic The color-changing device can show (orange-blue)-(yellow-blue)-green-blue multi-color change instead of only changing between orange-yellow-green-blue. Thus, the multicolor property of the all-solid-state electrochromic device is increased.

Example 3

Referring to FIG. 1 , the electrochromic device provided in this embodiment is a single-layer multi-color electrochromic device. Wherein, the first substrate 110 is an ordinary transparent glass sheet. The first conductive layer 120 is an indium tin oxide (ITO) film, which is used to communicate with an external power source and serves as a cathode electrode. The first electrochromic layer 130 is a molybdenum-doped vanadium pentoxide film. The electrolyte layer 140 is a polymer lithium salt solid electrolyte membrane. The second substrate 160 is also an ordinary transparent glass sheet. The second conductive layer 150 is an ITO film, which is used to communicate with an external power source and serves as an anode electrode. It uses epoxy resin 170 to laminate and seal two coated transparent glass sheets.

The manufacturing method of the above-mentioned single-layer electrochromic device comprises the following steps:

First, ordinary glass with an area of 2.5×2.5 cm ² cleaned by ultrasonic cleaning with acetone and absolute ethanol solution was used as the transparent first substrate 110 . The common glass has a transmittance of more than 80% in the range of visible light, and has a smooth surface and a planar structure.

Next, a layer of ITO thin film with a thickness of 50 nm-5 μm is deposited on the first substrate 110 by magnetron sputtering as the first conductive layer 120 , that is, the cathode conductive layer.

Then, use a mask plate or other covering plate to cover one corner of the ITO film as an electrode contact area, and deposit a molybdenum-doped vanadium pentoxide film with a thickness of 800nm on the ITO film by magnetron sputtering as the second electrode contact area. An electrochromic layer 130 .

Next, a layer of ITO thin film with a thickness of 50 nm-5 μm is also deposited on the second substrate 160 by magnetron sputtering as the second conductive layer 150 , that is, the anode conductive layer.

Then, a mask plate or other covering plates with the same covering function are also used to cover a corner of the ITO film (here referred to as the second conductive layer 150 ) as an electrode contact area. Epoxy resin 170 is used to separate the second conductive layer diaphragm and the molybdenum-doped vanadium pentoxide thin film diaphragm with a certain thickness of organic glass frame and seal with epoxy resin. At the same time, a small hole is reserved for the injection inlet of the electrolyte sol.

Finally, dissolve citric acid in absolute ethanol, then add ethyl orthosilicate, then add lithium carbonate and fully dissolve, finally add ethylene glycol, and keep the resulting colorless and transparent solution at 80°C for 24h (hours) to obtain Electrolyte sol (ie organic lithium ion sol). Then, a colorless and transparent organic lithium ion sol is injected between the two membranes with a syringe, and the sol is polymerized and completely cured at a preset baking temperature to form an organic lithium ion conductor film as the electrolyte of the electrochromic device. layer 140, thereby obtaining an all-solid-state single-layer multi-color electrochromic device.

By applying +3.0V, +1.0V, -1.0V and -3.0V square voltages between the cathode electrode and the anode electrode of the all-solid-state single-layer multi-color electrochromic device prepared in Example 1, it is known that the single The layer electrochromic device changes reversibly between orange-yellow-green-blue.

Correspondingly, the present invention also provides the application of any one of the above-mentioned electrochromic devices on a mobile terminal. Through power management and circuit integration, any one of the above-mentioned single-layer electrochromic devices or double-layer electrochromic devices is applied to the back shell of the mobile terminal, such as: the back shell of the mobile phone or the back shell of the tablet computer, etc., which improves the mobile terminal. The personalization and stability meet the individual color needs of consumers.

The above-mentioned embodiments only express several implementation modes of the present invention, and the description thereof is relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. an electrochromic device preparation method, is characterized in that, comprises the steps:

Adopt coating process at the first substrate surface depositing first conductive layer;

At described first conductive layer surface mask deposition first electrochromic layer;

Adopt described coating process on described first electrochromic layer surface successively deposit electrolyte layer and the second conductive layer; Or after described second conductive layer of the second substrate surface deposition, between described second conductive layer and described first electrochromic layer, prepare described dielectric substrate; Obtain individual layer electrochromic device;

Or, adopt described coating process to deposit described dielectric substrate, the second electrochromic layer and described second conductive layer successively on described first electrochromic layer surface; Or after described second substrate surface deposits described second conductive layer and described second electrochromic layer successively, between described second electrochromic layer and described first electrochromic layer, prepare described dielectric substrate; Obtain double-deck electrochromic device;

Described dielectric substrate is transparent solid-state organolithium ion conductor film.

2. electrochromic device preparation method according to claim 1, is characterized in that, prepares described dielectric substrate and comprises:

Between described second conductive layer and described first electrochromic layer, or inject between described second electrochromic layer and described first electrochromic layer or after injection electrolyte colloidal sol, under default baking temperature, be baked to described electrolyte colloidal sol be polymerized and solidify to form described transparent solid-state organolithium ion conductor film;

Wherein, described electrolyte colloidal sol is organolithium ion colloidal sol.

3. electrochromic device preparation method according to claim 2, is characterized in that, described default baking temperature is 50 DEG C-200 DEG C.

4. electrochromic device preparation method according to claim 1, is characterized in that, the depositing operation of described first electrochromic layer and described second electrochromic layer is electrochemical deposition process or magnetron sputtering deposition technique.

5. an electrochromic device, is characterized in that, adopts the electrochromic device preparation method preparation described in any one of Claims 1-4, comprises conductive layer, electrochromic layer and dielectric substrate;

Wherein, described dielectric substrate is transparent solid-state organolithium ion conductor film.

6. electrochromic device according to claim 5, is characterized in that, the transmitance of described transparent solid-state organolithium ion conductor film in visible-range is more than or equal to 80%; And,

The thickness of described transparent solid-state organolithium ion conductor film is 50nm ~ 5mm.

7. electrochromic device according to claim 6, is characterized in that, the ionic conductivity of described transparent solid-state organolithium ion conductor film is more than or equal to 1 × 10 ^-5s/cm.

8. electrochromic device according to claim 5, is characterized in that, described electrochromic layer is molybdenum doping vanadium pentoxide films; And,

Described molybdenum doping vanadium pentoxide films is the layer structure of [001] orientation.

9. electrochromic device according to claim 8, is characterized in that, in described molybdenum doping vanadium pentoxide films, the doping content of molybdenum is 5% ~ 10%mol; And,

The thickness of described molybdenum doping vanadium pentoxide films is 50nm ~ 5 μm.

10. the application on mobile terminals of the electrochromic device as described in any one of claim 5 to 9.