CN108549183A - Shell and preparation method, electronic equipment - Google Patents

Abstract

The invention discloses a casing, a preparation method and electronic equipment. The casing includes: a first substrate; a first transparent conductive layer, the first transparent conductive layer is arranged on the first substrate; an electrochromic layer, the electrochromic layer is arranged on the first transparent conductive layer layer away from the side of the first substrate, the electrochromic layer is formed by electropolymerization; an electrolyte layer, the electrolyte layer is arranged on the side of the electrochromic layer away from the first transparent conductive layer An ion storage layer, the ion storage layer is arranged on the side of the electrolyte layer away from the electrochromic layer; a second conductive layer, the second conductive layer is arranged on the ion storage layer away from the electrolyte layer and a flexible substrate disposed on a side of the second conductive layer away from the ion storage layer. By applying voltage to the first transparent conductive layer and the second conductive layer, the casing can have multiple colors, and the color changing time is short and the cost is low.

Description

Shell and preparation method, electronic device

technical field

The invention relates to the field of preparation of electronic equipment components, in particular, to a housing, a preparation method, and an electronic equipment.

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 electrochromic materials, which are widely used in information, electronics, energy, construction, and national defense. The current electrochromic glass usually has a structure of a glass substrate, a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a transparent conductive layer, and a glass substrate.

However, the current housings with electrochromic properties, their preparation methods, and electronic devices still need to be improved.

Contents of the invention

The present invention aims to solve one of the technical problems in the related art at least to a certain extent.

The present invention is accomplished based on the following findings of the inventors:

At present, most electrochromic glasses have disadvantages such as long discoloration time, monotonous discoloration, and high cost, and are not suitable for producing housings of electronic equipment (for example, cell phone battery covers). After in-depth research and a lot of experiments, the inventor found that this is mainly because the current electrochromic glass is usually formed of inorganic electrochromic materials and consists of two layers of glass substrates. Specifically, the current electrochromic glass is obtained by applying a translucent indium tin oxide or fluorine-doped tin oxide film to two pieces of glass to obtain conductivity, and then applying electrochromic tungsten oxide to one of the glasses, and then using A glue-like electrolyte bonds two pieces of glass together. When the voltage is connected, the color of the tungsten oxide coating is darkened, and when the voltage is disconnected, the color of the tungsten oxide coating becomes lighter, realizing the function of electrochromism. Among them, tungsten trioxide is an inorganic electrochromic material, and the electrochromic glass formed by it has a slow discoloration time. It takes at least 1 minute from the application of voltage to complete discoloration, and the discoloration time is too long, and the discoloration color is monotonous. In addition, the electrochromic glass is composed of two layers of glass substrates. The thickness of the glass substrates is too thick, and the two layers of glass substrates are transparent structures, which cannot cover the components inside the electronic equipment without discoloration. The cost of plating a transparent conductive layer on a glass substrate is relatively high. To sum up, the above-mentioned electrochromic glass is not suitable for producing casings of electronic equipment.

In view of this, in one aspect of the present invention, the present invention provides a housing. The casing includes: a first substrate; a first transparent conductive layer, the first transparent conductive layer is arranged on the first substrate; an electrochromic layer, the electrochromic layer is arranged on the first transparent conductive layer Layer away from the side of the first substrate, the electrochromic layer is formed by electropolymerization; an electrolyte layer, the electrolyte layer is arranged on the side of the electrochromic layer away from the first transparent conductive layer An ion storage layer, the ion storage layer is arranged on the side of the electrolyte layer away from the electrochromic layer; a second conductive layer, the second conductive layer is arranged on the ion storage layer away from the electrolyte layer and a flexible substrate disposed on a side of the second conductive layer away from the ion storage layer. Therefore, when a voltage is applied to the first transparent conductive layer and the second conductive layer, the casing can have multiple colors, and the color changing time is short and the cost is low.

In another aspect of the invention, the invention proposes a method of making a housing. According to an embodiment of the present invention, the method includes: respectively providing a first substrate and a flexible substrate; disposing a first transparent conductive layer on the first substrate, and disposing the first transparent conductive layer away from the first transparent conductive layer through electropolymerization. An electrochromic layer is formed on one side of a substrate; a second conductive layer, an ion storage layer and an electrolyte layer are sequentially arranged on the flexible substrate; and the first substrate provided with the electrochromic layer and the The flexible substrate is encapsulated with the electrolyte layer in contact with the electrochromic layer to form the housing. Therefore, a casing with multiple colors and short discoloration time can be obtained by using a simple process, and the production cost is low.

In another aspect of the invention, the invention proposes an electronic device. According to an embodiment of the present invention, the electronic device includes the above-mentioned casing, thus, the electronic device has all the features and advantages of the above-mentioned casing, which will not be repeated here. In general, the electronic device has various appearances, which improves user experience.

Description of drawings

FIG. 1 shows a schematic structural view of a housing according to an embodiment of the present invention;

Figure 2 shows a schematic structural view of a housing according to another embodiment of the present invention;

Figure 3 shows a schematic structural view of a housing according to another embodiment of the present invention;

Figure 4 shows a schematic structural view of a housing according to another embodiment of the present invention;

Figure 5 shows a schematic structural view of a housing according to another embodiment of the present invention;

Figure 6 shows a schematic structural view of a housing according to another embodiment of the present invention; and

Fig. 7 shows a schematic flowchart of a method for preparing a shell according to an embodiment of the present invention.

Reference signs:

100: first substrate; 200: first transparent conductive layer; 300: electrochromic layer; 400: electrolyte layer; 500: ion storage layer; 600: second conductive layer; 700: flexible substrate; 800: connecting wire; 900: insulating glue.

Detailed ways

Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary only for explaining the present invention and should not be construed as limiting the present invention.

In one aspect of the invention, the invention proposes a casing. According to an embodiment of the present invention, referring to FIG. 1, the housing includes: a first substrate 100, a first transparent conductive layer 200, an electrochromic layer 300, an electrolyte layer 400, an ion storage layer 500, a second conductive layer 600 and a flexible Substrate 700. Wherein, the first transparent conductive layer 200 is arranged on the first substrate 100, the electrochromic layer 300 is arranged on the side of the first transparent conductive layer 200 away from the first substrate 100, the electrochromic layer 300 is formed by electropolymerization, The electrolyte layer 400 is arranged on the side of the electrochromic layer 300 away from the first transparent conductive layer 200, the ion storage layer 500 is arranged on the side of the electrolyte layer 400 away from the electrochromic layer 300, and the second conductive layer 600 is arranged on the ion storage layer. 500 is away from the side of the electrolyte layer 400 , and the flexible substrate 700 is disposed on the side of the second conductive layer 600 away from the ion storage layer 500 . By applying voltage to the first transparent conductive layer and the second conductive layer, the casing can have multiple colors, and the color changing time is short and the cost is low.

For ease of understanding, the housing according to the embodiment of the present invention will be briefly described below:

As mentioned above, the current electrochromic glass is made conductive by applying a translucent indium tin oxide or fluorine-doped tin oxide film to two pieces of glass, and then applying electrochromic tungsten oxide to one of the glasses. Then use a glue-like electrolyte to bond the two pieces of glass together. When the voltage is connected, the color of the tungsten oxide coating will be darkened. After the voltage is disconnected, the color of the tungsten oxide coating will become lighter, realizing the function of electrochromism. Among them, tungsten trioxide is an inorganic electrochromic material, and the electrochromic glass formed by it has a slow discoloration time. It takes at least 1 minute from the application of voltage to complete discoloration, and the discoloration time is too long, and the discoloration color is monotonous. In addition, the electrochromic glass is composed of two layers of glass substrates. The thickness of the glass substrates is too thick, and the two layers of glass substrates are transparent structures, which cannot cover the components inside the electronic equipment without discoloration. The cost of plating a transparent conductive layer on a glass substrate is relatively high. To sum up, the above-mentioned electrochromic glass is not suitable for producing casings of electronic equipment.

According to an embodiment of the present invention, on the one hand, the housing is composed of an electrochromic layer formed by electropolymerization, and the organic electrochromic layer has a short color changing time and rich colors. Moreover, since the electrochromic layer is formed by electropolymerization, the shape of the formed electrochromic layer can be controlled easily through the shape of the counter electrode, that is, the shape of the first transparent conductive layer and the second conductive layer, so that Avoid additional trimming process, thereby simplifying the production process and reducing production costs.

On the other hand, the substrate is a glass substrate and a flexible substrate, and replacing the glass substrate in the prior art with a flexible substrate can reduce the thickness of the substrate, thereby reducing the overall thickness of the casing. Moreover, compared with preparing the conductive layer by sputtering on the glass substrate, the efficiency of preparing the conductive layer on the flexible substrate is higher and the cost is lower. Thus, the production efficiency can be improved and the cost can be reduced. And by designing the flexible substrate or the second conductive layer, the casing can be made non-transparent when no voltage is applied, which is suitable for electronic equipment: specifically, the flexible substrate is usually made of plastic material, which can be easily passed through the The plastic material is dyed to realize the shielding of other electronic device structures under the casing, and the dyeing cost of the plastic material is relatively low, and the color is adjustable and rich colors can be obtained. Moreover, the second conductive layer can also be formed of a metal with a certain metallic luster or color, so as to further enrich the appearance effect of the housing with electrochromic function.

To sum up, the casing can reduce the cost of the electronic device to which the casing is applied, enrich the appearance of the electronic device, and improve user experience.

The various structures of the housing are described in detail below according to specific embodiments of the present invention:

According to an embodiment of the present invention, the first substrate 100 is a transparent structure, specifically glass or plastic. Thus, the color produced by the electrochromic layer can be presented through the first transparent conductive layer and the first substrate. According to an embodiment of the present invention, the plastic forming the first substrate 100 may be polyethylene terephthalate or polycarbonate, thereby enhancing the toughness of the casing and making the casing resistant to falling.

According to an embodiment of the present invention, the first transparent conductive layer 200 may be made of indium tin oxide (ITO), thus, the first transparent conductive layer may have good conductivity and high transparency. According to an embodiment of the present invention, the square resistance of the first transparent conductive layer 200 is less than 50Ω, for example, may be less than 30Ω. Thus, on the one hand, the first transparent conductive layer has good electrical conductivity, the small square resistance can reduce energy loss, and control the discoloration time in a shorter range; on the other hand, the first transparent conductive layer With high transparency, it can better present the color produced by the electrochromic layer; on the other hand, controlling the square resistance of the first transparent conductive layer within the above range can make the electrochromic layer easier to electropolymerize to the first surface of the transparent conductive layer.

According to an embodiment of the present invention, the electrochromic layer 300 is formed by electropolymerization. Specifically, first put the electrolyte solution containing the organic electrochromic monomer into the three-electrode electrolytic cell, then use the first substrate 100 provided with the first transparent conductive layer 200 as the working electrode, and use platinum or gold as the auxiliary electrode, The electrochromic layer 300 is formed by using silver-silver chloride or saturated calomel as a reference electrode, followed by electropolymerization by a constant potential method or a constant current method. According to an embodiment of the present invention, the organic electrochromic monomer is an organic color-changing polymer material suitable for electropolymerization, such as polythiophenes, polyanilines, polycarbazoles, and the like. The electrochromic layer is an organic electrochromic layer, which presents a variety of colors and has a short discoloration time. It only takes 1 second from voltage application to complete discoloration, and the timeliness is improved. According to an embodiment of the present invention, the thickness of the electrochromic layer 300 is not greater than 200 nm. The inventors have found that when the thickness of the electrochromic layer is higher than the above value, the discoloration time will be prolonged and the electrochromic effect will be affected. Therefore, when the thickness of the electrochromic layer is set within the above-mentioned range, the discoloration time can be controlled within a shorter range and the timeliness can be improved.

According to an embodiment of the present invention, the electrolyte layer 400 is made of a gel material, specifically, the electrolyte layer 400 includes a gel material, a plasticizer, conductive ions and a solvent. Compared with the liquid electrolyte, the electrolyte layer formed by the gel-like material has the advantages of high stability and long service life, and will not cause bubbling or leakage of the electrolyte, thereby improving the service life of the shell. According to an embodiment of the present invention, the ions in the electrolyte layer 400 can be doped or dedoped with the organic electrochromic material in the electrochromic layer 300 , so that the color of the electrochromic layer 300 changes. Specifically, when a certain positive voltage is applied to the first transparent conductive layer 200 and the second conductive layer 600, the organic electrochromic material in the electrochromic layer 300 undergoes an oxidation reaction, loses electrons, and loses electrons in the electrochromic layer 300. The electrons in the electrochromic layer 300 migrate to the first transparent conductive layer 200, the negative ions in the electrolyte layer 400 migrate to the electrochromic layer 300, and are doped with the organic electrochromic material in the electrochromic layer 300, and the negative ions in the electrolyte layer 400 Positive ions migrate into the ion storage layer 500 , and electrons in the second conductive layer 600 migrate into the ion storage layer 500 , so that the color of the electrochromic layer 300 changes, and the entire system maintains charge balance. According to the embodiment of the present invention, when no voltage is applied to the casing, the color presented by the electrochromic layer 300 is the color that absorbs light itself; when a positive voltage is applied to the casing, the organic electricity in the electrochromic layer 300 The chromogenic material undergoes an oxidation reaction, the substance itself changes, and the spectrum it absorbs changes, thereby presenting another color. According to the embodiment of the present invention, when a negative voltage is applied to the shell after the color change occurs, the organic electrochromic material in the electrochromic layer 300 will undergo a reduction reaction, and the migrated ions and electrons will return to their original In the film layer, it changes back to the original color of the shell.

According to an embodiment of the present invention, the thickness of the electrolyte layer 400 is relatively thick. Thus, the electrochromic layer and the ion storage layer can be separated by the electrolyte layer, so that the migrating positive and negative ions will not gather quickly, and at the same time, the electrons in the first transparent conductive layer and the second conductive layer can be separated to ensure the electrical Stability of the color change of the chromogenic layer. According to a specific embodiment of the present invention, the thickness of the electrolyte layer 400 may be 50-300 μm. Thereby, the stability of discoloration of the electrochromic layer can be further improved. Designing the thickness of the electrolyte layer 400 within the above range can prevent defects such as breakdown caused by the electrolyte layer 400 being too thin, and can prevent the electrochromic time caused by the electrolyte layer 400 being too thick and the overall thickness of the casing being relatively long. Thick and other bad problems.

According to an embodiment of the present invention, the thickness of the ion storage layer 500 may be on the order of nanometers. Thereby, the color of the electrochromic layer can be changed. According to an embodiment of the present invention, when the ions in the ion storage layer 500 present a certain color, the thickness of the ion storage layer 500 should not be too thick: when the thickness of the ion storage layer 500 is thicker, its color is darker, and the color of the ion storage layer 500 is darker when the casing is not When a voltage is applied, the color of the ion storage layer 500 will pass through the electrolyte layer 400, the electrochromic layer 300, the first transparent conductive layer 200 and the first substrate 100, so that the casing presents a certain color, which affects the discoloration effect of the casing . Thus, the thickness of the ion storage layer can be reasonably designed according to the above two conditions, and the specific thickness value of the ion storage layer is not particularly limited, as long as the color of the electrochromic layer can be changed and the entire housing can It is relatively transparent, that is, it does not affect the discoloration effect of the shell. For example, according to specific embodiments of the present invention, the thickness of the pure solid content in the ion storage layer 500 may be 100-700 nm. For example, when the ion storage layer 500 exhibits a certain blue color, the thickness of the pure solid content in the ion storage layer 500 may be 200-300 nm. According to an embodiment of the present invention, when the ion storage layer 500 is in a transparent state, the thickness of the ion storage layer 500 can be increased without affecting the electrochromic efficiency. At this time, the thickness of the ion storage layer 500 can be 10 μm or greater. 10 μm, as long as it does not affect the electrochromic efficiency. For example, the thickness of the ion storage layer before drying formed by spin coating may be 5 μm, and the thickness of the ion storage layer after drying may be 1 μm.

The specific material of the second conductive layer is not particularly limited, as long as the second conductive layer has good electrical conductivity, those skilled in the art can design according to specific conditions. For example, according to an embodiment of the present invention, the second conductive layer 600 may be formed of a transparent conductive material, specifically, indium tin oxide or nano-silver. When the second conductive layer is formed of a transparent conductive material, the second conductive layer can be designed to have a small square resistance to ensure that it has good conductivity and reduce energy consumption. At this time, the transparency of the second conductive layer can be ignored. Require. According to other embodiments of the present invention, the second conductive layer 600 may also be formed of an opaque conductive material, specifically, metal materials such as aluminum and copper. When the second conductive layer is formed of a metal material, on the one hand, the metal material has good conductivity, and on the other hand, the metal material is an opaque material, so that the components in the electronic device can be shielded when no voltage is applied to the housing, ensuring The appearance of electronic equipment.

According to an embodiment of the present invention, the flexible substrate 700 may be polyethylene terephthalate or polycarbonate. On the one hand, the thickness of the flexible substrate is small, the efficiency of plating the second conductive layer on the flexible substrate is high, and the cost is low, and the flexible substrate can be used as a coil material for plating the second conductive layer. , the cost of the flexible substrate is lower than that of the glass substrate, further reducing the cost. According to an embodiment of the present invention, when the second conductive layer 600 is formed of a transparent conductive material, inks of different colors are printed on the surface of the flexible substrate 700 or different texture effects are set to cover the components in the electronic device, and further Enrich the final rendering of the shell.

According to an embodiment of the present invention, referring to FIGS. 2-6 , the casing may further include insulating glue 900 . In this way, the casing can be packaged, so that the casing presents a good appearance effect when a voltage is applied. According to an embodiment of the present invention, the insulating glue 900 may be 3M glue. The location of the insulating glue is not particularly limited, as long as the above effects are achieved, those skilled in the art can design according to specific conditions. For example, according to an embodiment of the present invention, with reference to FIGS. layer 500, and seal the electrochromic layer 300, the electrolyte layer 400 and the ion storage layer 500. According to other embodiments of the present invention, referring to FIG. 6 , the insulating glue 900 is disposed between the first substrate 100 and the flexible substrate 700, and is wound around the first transparent conductive layer 200, the electrochromic layer 300, and the electrolyte layer 400. , the ion storage layer 500 and the periphery of the second conductive layer 600 , and seal the electrochromic layer 300 , the electrolyte layer 400 and the ion storage layer 500 . Thus, the electrochromic layer can be sealed and insulated to prevent interference from the external environment.

According to an embodiment of the present invention, referring to FIGS. 2-6 , the casing may further include: a connecting wire 800 connected to the first transparent conductive layer 200 and the second conductive layer 600 . Thus, the electrochromic layer can be controlled to change color by applying voltage to the first transparent conductive layer and the second conductive layer through the control circuit. There are no particular restrictions on the specific material of the connecting wire and its connection with the first transparent conductive layer and the second conductive layer. For example, according to an embodiment of the present invention, at least the first transparent conductive layer 200 and the second conductive layer 600 One of them is formed through the same patterning process as the connecting wire 800 . Specifically, referring to FIG. 2 and FIG. 3, the connecting wire 800 connected to the first transparent conductive layer 200 has the same material as the first transparent conductive layer 200, and is formed by the same patterning process as the first transparent conductive layer 200; The connecting wire 800 connecting the two conductive layers 600 has the same material as the second conductive layer 600 , and is formed by the same patterning process as the second conductive layer 600 . Thus, the connecting wire can be made into a structure integrated with the first transparent conductive layer or the second conductive layer, which simplifies the production process. According to an embodiment of the present invention, when the connecting conductive layer 800 and the conductive layer are formed by the same patterning process, the insulating glue 900 is arranged between the first transparent conductive layer 200 and the second conductive layer 600, and seals the electrochromic layer 300 and the electrolyte layer. 400 and ion storage layer 500. The position of the insulating glue 900 is not particularly limited, it can be flush with the first transparent conductive layer 200 and the second conductive layer 600 (refer to FIG. The conductive layer 200 and the second conductive layer 600 are arranged between the two connecting wires 800 (refer to FIG. 3 ) to enhance sealing.

According to other embodiments of the present invention, referring to FIG. 4 and FIG. 5 , the connecting wire 800 is a copper tape, the copper tape extends to the side away from the electrochromic layer 300 , and the edge of the copper tape is close to the side of the electrochromic layer 300 , there is an overlapping area between the edges of the conductive layer (the first transparent conductive layer 200 and the second conductive layer 600 ) connected thereto. Thus, electrical conduction can be achieved with the copper tape. According to an embodiment of the present invention, when the connecting conductive layer 800 is a copper tape, the insulating glue 900 is disposed between the first transparent conductive layer 200 and the second conductive layer 600, and is aligned with the first transparent conductive layer 200 and the second conductive layer 600 flat, and seal the electrochromic layer 300, the electrolyte layer 400, and the ion storage layer 500 (see FIG. 4). Or, according to other embodiments of the present invention, the insulating glue 900 on one side of the copper tape is disposed between the first transparent conductive layer 200, the second conductive layer 600 and between two copper tapes (refer to FIG. 5 ) to enhance sealing.

According to an embodiment of the present invention, the connecting wire 800 can also be a metal wire. Referring to FIG. On the periphery of layer 300 , electrolyte layer 400 , ion storage layer 500 , and second conductive layer 600 , metal wires (connecting wires 800 ) pass through insulating glue 900 and extend to the side of insulating glue 900 away from electrochromic layer 300 . Thus, electrical conduction can be achieved via the metal wire. In addition, the insulating glue 900 can also be used to further improve the bonding between the metal wire and the conductive layer (including the first transparent conductive layer 200 and the second conductive layer 600): for example, the metal wire can be bonded to the conductive layer with conductive glue first. layer, or realize the electrical connection between the metal wire and the conductive layer by means including but not limited to heat fusion, welding, etc. Subsequently, insulating glue 900 may be disposed at the contact point between the metal wire and the conductive layer, so as to prevent short circuit at the contact point between the metal wire and the conductive layer. The specific material of the metal wire is not particularly limited, as long as it can realize electrical conduction, those skilled in the art can design according to the specific situation. For example, according to specific embodiments of the present invention, the metal wires may be copper wires.

In another aspect of the invention, the invention proposes a method of making a housing. According to an embodiment of the present invention, the housing prepared by this method may be the housing described above, and thus, the housing prepared by this method may have the same features and advantages as the housing described above, which will not be repeated here. According to an embodiment of the present invention, referring to FIG. 7, the method includes:

S100: providing a first substrate and a flexible substrate respectively

According to an embodiment of the present invention, in this step, the first substrate and the flexible substrate are respectively provided. According to an embodiment of the present invention, the first substrate may be glass or plastic. Thus, the color produced by the electrochromic layer can be displayed through the first substrate. According to an embodiment of the present invention, the flexible substrate may be polyethylene terephthalate or polycarbonate. On the one hand, the thickness of the flexible substrate is small, which can reduce the overall thickness of the shell, and the efficiency of plating the second conductive layer on the flexible substrate in the subsequent steps is high, and the cost is low, and the flexible substrate can be used as a roll The material is used to plate the second conductive layer. When the coating is defective, the cost of the flexible substrate is lower than that of the glass substrate, further reducing the cost.

S200: Forming an electrochromic layer by electropolymerization

According to an embodiment of the present invention, in this step, the electrochromic layer is formed by electropolymerization. According to an embodiment of the present invention, before forming the electrochromic layer, firstly, a first transparent conductive layer is formed on the first substrate. The first transparent conductive layer can be indium tin oxide, thus, the first transparent conductive layer can have good conductivity and high transparency. According to an embodiment of the present invention, the first transparent conductive layer can be formed by sputtering. When forming the first transparent conductive layer on the glass substrate, high-temperature sputtering is used, and the temperature is higher than 400 ° C. The first transparent conductive layer is formed on the plastic substrate. Low-temperature sputtering is used for the conductive layer, and the temperature is lower than 100°C. Thus, the first transparent conductive layer can be formed using a simple process. According to a specific embodiment of the present invention, the temperature for forming the first transparent conductive layer on the plastic substrate by sputtering may be 60°C, 70°C, 80°C or 90°C.

Regarding the square resistance of the first transparent conductive layer, it has been described in detail above, and will not be repeated here. For example, according to an embodiment of the present invention, the square resistance of the first transparent conductive layer is less than 50Ω, for example, may be less than 30Ω. Thus, on the one hand, the first transparent conductive layer has good electrical conductivity, the small square resistance can reduce energy loss, and control the discoloration time in a shorter range; on the other hand, the first transparent conductive layer With high transparency, it can better present the color produced by the electrochromic layer; on the other hand, controlling the square resistance of the first transparent conductive layer within the above range can make the electrochromic layer easier to electropolymerize to the first surface of the transparent conductive layer.

According to an embodiment of the present invention, after the first transparent conductive layer is formed on the first substrate, an electrochromic layer is formed on the side of the first transparent conductive layer away from the first substrate by electropolymerization. Specifically, firstly, the electrolytic solution containing the organic electrochromic monomer is put into a three-electrode electrolytic cell, then the first substrate provided with the first transparent conductive layer is used as the working electrode, platinum or gold is used as the auxiliary electrode, and silver is used as the auxiliary electrode. - the silver chloride or saturated calomel electrode is the reference electrode, the first transparent conductive layer is directly opposite to the platinum or gold electrode, and the distance between the two is less than 3cm, and then the electropolymerization is carried out by a constant potential method or a constant current method, An electrochromic layer is formed. The electrochromic layer is an organic electrochromic layer, which presents a variety of colors and has a short discoloration time. It only takes 1 second from voltage application to complete discoloration, and the timeliness is improved. The specific value of the distance between the first transparent conductive layer and the platinum or gold electrode can be adjusted according to the actual electropolymerization effect. According to an embodiment of the present invention, when electropolymerization is performed by a constant potential method, the polymerization voltage does not exceed 2V. The specific value of the polymerization voltage can be designed according to the organic electrochromic monomer, and the polymerization time can be designed according to the applied polymerization voltage to ensure a good polymerization effect.

According to an embodiment of the present invention, the thickness of the electrochromic layer is not greater than 200 nm. The inventors have found that when the thickness of the electrochromic layer is higher than the above value, the discoloration time will be prolonged and the electrochromic effect will be affected. Therefore, when the thickness of the electrochromic layer is set within the above-mentioned range, the discoloration time can be controlled within a shorter range and the timeliness can be improved.

S300: sequentially disposing a second conductive layer, an ion storage layer, and an electrolyte layer on a flexible substrate

According to an embodiment of the present invention, in this step, the second conductive layer, the ion storage layer and the electrolyte layer are sequentially disposed on the flexible substrate. According to an embodiment of the present invention, the second conductive layer is formed on the flexible substrate by sputtering, and the sputtering temperature is lower than 100° C. Thus, the second conductive layer can be formed using a simple process. According to a specific embodiment of the present invention, the temperature for forming the second conductive layer on the flexible substrate by sputtering may be 60°C, 70°C, 80°C or 90°C. The material of the second conductive layer has been described in detail above, and will not be repeated here. For example, according to an embodiment of the present invention, the second conductive layer may be formed of a transparent conductive material, specifically, indium tin oxide or nano-silver. When the second conductive layer is formed of a transparent conductive material, the second conductive layer can be designed to have a small square resistance to ensure that it has good conductivity and reduce energy consumption. At this time, the transparency of the second conductive layer can be ignored. Require. At this time, different texture effects or inks of different colors can be set on the flexible substrate, and the components in the electronic device can be blocked when the housing is not powered, so as to ensure the appearance of the electronic device. According to other embodiments of the present invention, the second conductive layer may also be formed of an opaque conductive material, specifically, metal materials such as aluminum and copper. When the second conductive layer is formed of a metal material, on the one hand, the metal material has good conductivity, and on the other hand, the metal material is an opaque material, so that the components in the electronic device can be shielded when no voltage is applied to the housing, ensuring The appearance of electronic equipment.

According to an embodiment of the present invention, the ion storage layer can be formed by spin coating, curtain coating, roll coating, scraping coating, dip coating, spray coating or silk screen printing. Specifically, the ink containing the polymer of the ion storage layer is evenly coated on the second The second conductive layer is away from the side of the flexible substrate, and the thickness of the formed ion storage layer can be nanometer level. The design principle of the thickness of the ion storage layer has been described in detail above, and will not be repeated here. For example, according to specific embodiments of the present invention, the thickness of the pure solid content in the ion storage layer may be 100-700 nm. For example, when the ion storage layer exhibits a certain blue color, the thickness of the pure solid content in the ion storage layer may be 200-300 nm. According to an embodiment of the present invention, when the ion storage layer is in a transparent state, the thickness of the ion storage layer can be increased without affecting the electrochromic efficiency. At this time, the thickness of the ion storage layer can be 10 μm or greater, as long as It is sufficient that the electrochromic efficiency is not affected. For example, the thickness of the ion storage layer before drying formed by spin coating may be 5 μm, and the thickness of the ion storage layer after drying may be 1 μm.

According to an embodiment of the present invention, the electrolyte layer can be evenly coated on the side of the ion storage layer away from the second conductive layer by screen printing, and then dried at 40-60° C. to obtain the electrolyte layer. According to a specific embodiment of the present invention, the drying temperature may be 50°C. Compared with the liquid electrolyte, the electrolyte layer formed by the gel-like material has the advantages of high stability and long service life, and will not cause bubbling or leakage of the electrolyte, so that the service life of the shell can be further improved. According to an embodiment of the present invention, the thickness of the electrolyte layer may be 50-300 μm. As a result, the migrating positive and negative ions can be prevented from gathering quickly, thereby further improving the stability of the color change of the electrochromic layer. Designing the thickness of the electrolyte layer within the above range can prevent defects such as breakdown caused by too thin an electrolyte layer, and prevent defects such as long electrochromic time and a thicker overall thickness of the casing caused by an excessively thick electrolyte layer. question.

S400: Encapsulate the first substrate provided with the electrochromic layer and the flexible substrate provided with the electrolyte layer, the electrolyte layer is in contact with the electrochromic layer, so as to form a housing

According to an embodiment of the present invention, in this step, the first substrate provided with the electrochromic layer and the flexible substrate provided with the electrolyte layer are packaged, and the electrolyte layer is in contact with the electrochromic layer to form a casing. According to an embodiment of the present invention, the encapsulation process can be realized through the following steps: an insulating glue is arranged on the periphery of the electrochromic layer, the electrolyte layer, and the ion storage layer, and the first substrate is opposite to the flexible substrate. Glue connected. Thus, the electrochromic layer can be sealed and insulated to prevent interference from the external environment.

The type of the insulating glue is not particularly limited. For example, according to the embodiment of the present invention, the insulating glue can be an insulating tape, and the thickness of the insulating tape is consistent with the sum of the thicknesses of the electrochromic layer, the electrolyte layer and the ion storage layer. Thereby, sealing of the electrochromic layer, the electrolyte layer and the ion storage layer can be achieved. According to other embodiments of the present invention, the insulating glue can also be glue, and the insulating glue is arranged on the periphery of the first transparent conductive layer and the second conductive layer by dispensing to realize the electrochromic layer, the electrolyte layer and the ion Sealing of the storage layer.

According to an embodiment of the present invention, when forming the first transparent conductive layer and the second conductive layer, connecting wires can also be formed synchronously, and the insulating glue is disposed on a side of the connecting wires away from the conductive layer. According to an embodiment of the present invention, the electrochromic layer is formed by electropolymerization. In the process of forming the electrochromic layer, a mask plate can be provided at the position where the first transparent conductive layer needs to form a connecting wire, thereby preventing An electrochromic layer is formed at the position where the first transparent conductive layer needs to be provided with connecting wires. Alternatively, after the electrochromic material is formed on the first transparent conductive layer (including the position where the connecting wire needs to be set) by electropolymerization, the electrochromic material at the position where the connecting wire needs to be set is removed to form the electrochromic layer.

According to a specific embodiment of the present invention, the connecting wire and at least one of the first transparent conductive layer and the second conductive layer are formed through the same patterning process: the connecting wire connected to the first transparent conductive layer The conductive layer is made of the same material and formed by the same patterning process as the first transparent conductive layer; the connecting wire connected to the second conductive layer has the same material as the second conductive layer and is formed by the same patterning process as the second conductive layer. Thus, the connecting wire can be made into a structure integrated with the first transparent conductive layer or the second conductive layer, which simplifies the production process.

According to other embodiments of the present invention, the formed connecting wires can also be copper tapes, the copper tapes extend to the side away from the electrochromic layer, and the edge of the copper tape is close to the side of the electrochromic layer, and the conductive wires connected to it There is an overlapping area between the edges of the layers (the first transparent conductive layer and the second conductive layer). Thus, electrical conduction can be achieved with the copper tape.

According to an embodiment of the present invention, when using the same patterning process as the conductive layer to form the connecting wire, or when using copper tape as the connecting wire, the insulating glue can be arranged between the first transparent conductive layer and the second conductive layer, or the The insulating glue on the side where the connecting wire is arranged is arranged between the first transparent conductive layer, the second conductive layer and between the two connecting wires to enhance sealing.

According to other embodiments of the present invention, the connecting wires may also be metal wires, and the metal wires and the conductive layer are connected by insulating glue. Specifically, the insulating glue is arranged between the first substrate and the flexible substrate, and is wound around the periphery of the first transparent conductive layer, the electrochromic layer, the electrolyte layer, the ion storage layer, and the second conductive layer, and the metal wires pass through The insulating glue extends to the side of the insulating glue away from the electrochromic layer. Thus, electrical conduction can be achieved via the metal wire. The specific material of the metal wire is not particularly limited, as long as it can realize electrical conduction, those skilled in the art can design according to the specific situation. For example, according to specific embodiments of the present invention, the metal wires may be copper wires.

It should be noted that the first transparent conductive layer and the electrochromic layer can be sequentially disposed on the first substrate, and then the second conductive layer, ion storage layer and electrolyte layer can be sequentially disposed on the flexible substrate; The second conductive layer, the ion storage layer and the electrolyte layer are sequentially arranged on the flexible substrate, and then the first transparent conductive layer and the electrochromic layer are sequentially arranged on the first substrate. That is to say, the order of forming the first substrate and the flexible substrate with each layer structure is not particularly limited, as long as the required formation is formed on the two substrates (including the first substrate and the flexible substrate) respectively before packaging. structure.

In another aspect of the invention, the invention proposes an electronic device. According to an embodiment of the present invention, the electronic device includes the casing described above, thus, the electronic device has all the features and advantages of the casing described above, which will not be repeated here. In general, the electronic device has various appearances, which improves user experience. According to a specific embodiment of the present invention, the electronic device includes a casing, a display, and structures such as a main board and a battery arranged in the casing. Specifically, the casing may include a first substrate, a first transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer, a second conductive layer, and a flexible substrate. The voltage control circuit is used to control the voltage between the first transparent conductive layer and the second conductive layer to change the color of the electrochromic layer. The electrochromic layer can display different colors under different voltages, so as to obtain an appearance effect Electronic devices with variable housings.

In the description of the present invention, the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", " The orientations or positional relationships indicated by "top", "bottom", etc. are based on the orientations or positional relationships shown in the drawings, and are only for the convenience of describing the present invention and do not require that the present invention must be constructed and operated in a specific orientation, so they cannot be understood as Limitations on the Invention.

In the description of this specification, description with reference to the terms "one embodiment", "another embodiment", etc. means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention . In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.

Claims (26)

1. a kind of shell, which is characterized in that including：

First substrate；

First transparency conducting layer, first transparency conducting layer are arranged on the first substrate；

Electrochromic layer, the electrochromic layer are arranged in the side of first transparency conducting layer far from the first substrate, The electrochromic layer is formed by electropolymerization；

Electrolyte layer, the electrolyte layer are arranged in side of the electrochromic layer far from first transparency conducting layer；

Ion storage layer, the ion storage layer are arranged in side of the electrolyte layer far from the electrochromic layer；

Second conductive layer, second conductive layer are arranged in side of the ion storage layer far from the electrolyte layer；And

Flexible substrate, the flexible substrate are arranged in the side of second conductive layer far from the ion storage layer.

2. shell according to claim 1, which is characterized in that the thickness of the electrochromic layer is not more than 200nm.

3. shell according to claim 1, which is characterized in that the first substrate is glass or plastic cement.

4. shell according to claim 1, which is characterized in that first transparency conducting layer is made of tin indium oxide, institute The sheet resistance for stating the first transparency conducting layer is less than 50 Ω.

5. shell according to claim 1, which is characterized in that the flexible substrate be polyethylene terephthalate or Person's makrolon.

6. shell according to claim 1, which is characterized in that the thickness of the electrolyte layer is 50-300 μm.

7. shell according to claim 1, which is characterized in that the electrolyte layer is made of colloidal material, described Colloidal material includes glue material, plasticizer, conductive ion and solvent.

8. shell according to claim 1, which is characterized in that further comprise：

Insulating cement, the insulating cement are arranged between the first substrate and the flexible substrate, around being located at the electroluminescent change The periphery of chromatograph, the electrolyte layer, the ion storage layer, and by the electrochromic layer, the electrolyte layer and institute State ion storage layer sealing.

9. shell according to claim 8, which is characterized in that further comprise：

Connecting wire, the connecting wire are connected with first transparency conducting layer and second conductive layer.

10. shell according to claim 9, which is characterized in that first transparency conducting layer and second conduction At least one of layer is by being formed with a patterning processes with the connecting wire.

11. shell according to claim 9, which is characterized in that the connecting wire is copper adhesive tape, the side of the copper adhesive tape Edge has overlapping region between the edge for the conductive layer being connect with it.

12. according to claim 10 or 11 any one of them shells, which is characterized in that the insulating cement is arranged described first Between transparency conducting layer and second conductive layer, and seal the electrochromic layer, the electrolyte layer and it is described from Sub- storage layer.

13. shell according to claim 10, which is characterized in that the connecting wire is plain conductor, and the metal is led Line passes through the insulating cement and extends to side of the insulating cement far from the electrochromic layer.

14. a kind of method preparing shell, which is characterized in that including：

First substrate and flexible substrate are provided respectively；

First transparency conducting layer is set on the first substrate, by electropolymerization in first transparency conducting layer far from described The side of first substrate forms electrochromic layer；

The second conductive layer, ion storage layer and electrolyte layer are set gradually in the flexible substrate；And

The first substrate of the electrochromic layer will be provided with and be provided with the flexible substrate of the electrolyte layer It is packaged, the electrolyte layer is in contact with the electrochromic layer, to form the shell.

15. according to the method for claim 14, which is characterized in that the electropolymerization is under three-electrode system using permanent electricity What position method or galvanostatic method carried out.

16. according to the method for claim 14, which is characterized in that first transparency conducting layer and second conduction Layer is formed by sputter.

17. according to the method for claim 16, which is characterized in that the first substrate is glass or plastic cement, described The temperature that first transparency conducting layer is arranged on glass is higher than 400 DEG C, and first electrically conducting transparent is arranged on the plastic cement The temperature of layer is less than 100 DEG C；

The temperature that second conductive layer is arranged in the flexible substrate is less than 100 DEG C.

18. according to the method for claim 14, which is characterized in that the ion storage layer is by spin coating, showering, rolling What painting, blade coating, dip-coating, spraying or silk-screen were formed.

19. according to the method for claim 14, which is characterized in that the electrolyte layer is made of colloidal material, institute It includes glue material, plasticizer, conductive ion and solvent to state colloidal material, and the thickness of the electrolyte layer is 50-300 μm, described Electrolyte layer is formed by silk-screen printing.

20. according to the method for claim 19, which is characterized in that form the electrolyte layer and further comprise：

The colloidal material is dried at 40-60 DEG C.

21. according to the method for claim 14, which is characterized in that it is described encapsulation through the following steps that realize：

In the electrochromic layer, the periphery setting insulating cement of the electrolyte layer, the ion storage layer；

The first substrate and the flexible substrate are arranged oppositely, and are connected by the insulating cement.

22. according to the method for claim 21, which is characterized in that the insulating cement is insulating tape, the insulating tape Thickness, it is consistent with the sum of the thickness of the electrochromic layer, the electrolyte layer, the ion storage layer.

23. according to the method for claim 21, which is characterized in that the insulating cement is glue, transparent is led described first The insulating cement, which is arranged, in the periphery of electric layer and second conductive layer is realized by dispensing.

24. according to the method for claim 21, which is characterized in that form first transparency conducting layer and described second Further comprise when conductive layer：

It synchronizes to form connecting wire, the insulating cement is arranged in side of the connecting wire far from conductive layer.

25. according to the method for claim 21, which is characterized in that further comprise before the encapsulation：

The connecting wire being connected with first transparency conducting layer and second conductive layer, the connecting wire is respectively set For metal wire, the encapsulation further comprises：Enable that the metal wire passes through the insulating cement and to extend to the insulating cement separate The side of the electrochromic layer.

26. a kind of electronic equipment, which is characterized in that including claim 1-13 any one of them shells.