An electrochromic device and its application

Abstract

The present invention provides an electrochromic device and its application, comprising a first transparent conductive layer, a color-changing layer, and a second transparent conductive layer; wherein the first transparent conductive layer comprises a first conductive portion and a second conductive portion, and the second transparent conductive layer comprises a third conductive portion and a fourth conductive portion; the color-changing layer is located between the first and third conductive portions, and the three together form a film body; the second conductive portion is bent to form a first curved portion, and the fourth conductive portion is bent to form a second curved portion; wherein electrode leads are respectively provided on the first and second curved portions. The electrochromic device provided by the present invention can be used not only as a display screen protective film, but also in the back shell or protective shell of electronic terminal devices, and can be used in electronic terminal devices with cameras to achieve an integrated color-changing effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromism and relates to an electrochromism device and applications thereof. Background Art

[0002] With the continuous advancement of technology, the variety of electronic devices, such as mobile phones, is increasing. When purchasing these devices, consumers are increasingly focused on both the device's performance and its diverse and personalized appearance. Currently, some manufacturers offer a variety of colors on the exterior casing of their devices to attract consumers. However, once the colors are set, these casings remain fixed, providing a temporary sense of novelty but failing to attract consumers in the long term. Consequently, more consumers are opting for personalized covers over their phones. However, some consumers often replace their covers after a period of use, leaving the original cover likely to be discarded. This significantly wastes materials, is environmentally unfriendly, and increases the purchase cost for consumers.

[0003] Electrochromic devices, which can undergo stable and reversible changes in color and / or transmittance under an applied electric field, have enormous applications in smart homes and consumer electronics. Currently, the transparency of smartphone back covers, or the independent housings that wrap around the back of a phone, cannot be altered, and the pattern or color remains fixed. Electrochromic devices can meet these requirements.

[0004] CN109634018A discloses a color-changing cover plate, comprising a sequentially stacked glass substrate, an optical adhesive layer, and an electrochromic device. The electrochromic device comprises a first film layer and a second film layer arranged in parallel and offset configurations. A first transparent conductive layer is disposed on the surface of the first film layer facing the second film layer, and a second transparent conductive layer is disposed on the surface of the second film layer facing the first film layer. An electrochromic material layer and an electrolyte layer are disposed between the first and second transparent conductive layers. The electrolyte layer may be a gel electrolyte layer, a fully solid electrolyte layer, or a liquid electrolyte layer. Electrode leads are disposed at offset positions along the edges of the first and second transparent conductive layers. The electrode leads are electrically connected to a flexible circuit board via conductive adhesive, and the flexible circuit board is electrically connected to the mainboard of a mobile terminal. Although the electrochromic film provided in this patent has color-changing properties, its edges require wiring for connection to external circuitry and packaging, resulting in a border around the edge of the electrochromic film that prevents color change. Consequently, when the electrochromic film changes color, the color change of the mobile phone back cover cannot be integrated. At the same time, since some current electronic terminal devices, such as mobile phones and tablets, have some special functional areas, such as fingerprint areas, cameras, flashes, etc., some functional areas are protruding, such as protruding cameras, the current electrochromic films cannot meet application requirements.

[0005] Therefore, it is necessary to develop an electrochromic device that can, on the one hand, be compatible with the functional areas of current electronic devices and, on the other hand, achieve an integrated color-changing effect. Summary of the Invention

[0006] The object of the present invention is to provide an electrochromic device and its application. The electrochromic device provided by the present invention can be used not only as a display screen, but also as a rear shell or protective shell of an electronic terminal device, and can be used in an electronic terminal device with a camera to achieve an integrated color change effect. The present invention preferably uses a flexible all-solid-state electrochromic device, wherein each layer structure included is a flexible solid-state structure, and the electrolyte layer is also preferably a flexible solid-state electrolyte layer; the flexible all-solid-state electrochromic device can be applied to both planar structures and bendable and foldable structures.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an electrochromic device comprising a first transparent conductive layer, a color-changing layer, and a second transparent conductive layer.

[0009] Among them, the first transparent conductive layer includes a first conductive part and a second conductive part, the second transparent conductive layer includes a third conductive part and a fourth conductive part, the color-changing layer is located between the first conductive part and the third conductive part, and the three together form the main body of the film, the second conductive part is bent to form a first bent part, and the fourth conductive part is bent to form a second bent part.

[0010] Wherein, the first bending portion and the second bending portion are respectively provided with electrode leads.

[0011] The present invention designs the part of the conductive layer where the wiring connection position needs to be set as a film edge bending portion (a first bending portion and a second bending portion). In actual application, the film edge bending portion can correspond to the frame of the electronic terminal device, for example, it can be any one or at least two of the left frame, right frame, upper frame or lower frame. For example, the first bending portion and the second bending portion can jointly form the lower frame; or the first bending portion can form the left frame and the second bending portion can form the right frame.

[0012] When the electrochromic device provided by the present invention is used, the film main body can be attached to the back panel of the electronic terminal device as the main body, or can be used as the display screen of the electronic terminal device, while the first curved portion and the second curved portion are attached to the frame of the electronic terminal device, thereby achieving an integrated electrochromic effect.

[0013] Preferably, the electrochromic device further comprises a first protective layer located on a side of the first transparent conductive layer away from the color-changing layer.

[0014] Preferably, the first protective layer is made of transparent material.

[0015] Preferably, the first protective layer includes a first protective portion and a second protective portion, the first protective portion covers the first conductive portion, the second protective portion covers the second conductive portion, and the second protective portion is made of a non-transparent material.

[0016] Preferably, the electrochromic device further comprises a second transparent protective layer located on a side of the second transparent conductive layer away from the color-changing layer.

[0017] In order to protect the conductive layers on both sides of the electrochromic device, a transparent protective layer is provided. On the one hand, it can protect the conductive layer from damage, and on the other hand, the transparent material does not affect the application of the electrochromic device.

[0018] The protective layer can be arranged on the side of the first transparent conductive layer away from the color-changing layer, or on the side of the second transparent conductive layer away from the color-changing layer, or can be arranged on both sides at the same time.

[0019] Preferably, the color-changing layer includes an electrochromic material layer, an electrolyte layer and an ion storage layer, and the electrochromic material layer is located between the first transparent conductive layer and the electrolyte layer.

[0020] Preferably, the first transparent conductive layer includes a first transparent substrate and a first conductive layer, the second transparent conductive layer includes a second transparent substrate and a second conductive layer, the first conductive layer is located between the first transparent substrate and the color-changing layer, and the second conductive layer is located between the second transparent substrate and the color-changing layer.

[0021] Because in the actual preparation process, the conductive layer is directly prepared on the substrate and is also applied directly with the substrate, therefore, in the present invention, we collectively name the substrate and the conductive layer as a transparent conductive layer.

[0022] Preferably, the film body is provided with a first blind hole and / or a first through hole.

[0023] Through holes, also known as vias, are holes that go all the way from the top layer to the bottom layer. Blind holes are holes that can only be seen from one side, meaning they are set on one surface but do not go through all layers.

[0024] In order to match electronic terminal devices with cameras, other functional areas that need to capture light images, or that need to have openings (such as fingerprint sensing areas), the present invention sets through holes or blind holes on the electrochromic device. If the camera is a flat camera, a through hole can be set so that the incident light is not blocked. A blind hole can also be set. Since all layers except the color-changing layer are made of transparent materials, they will not affect the incident light. When the camera is a protruding camera or other protruding functional area, the height of its blind hole needs to match the height of the protruding part of the electronic terminal device. On the one hand, it can accommodate the protruding part, and on the other hand, it does not affect its use (such as a protruding camera). The area corresponding to the protruding part can also be set as an electrochromic device. When incident light is required, this area can be transparent.

[0025] In the present invention, it can be implemented specifically through the following embodiments:

[0026] Preferably, if Figure 1 As shown, a through hole is provided on the main body of the film so that the incident light of the protruding part of the electronic terminal device (such as a camera) is not blocked.

[0027] Preferably, if Figure 2 As shown, the electrochromic device includes a first transparent protective layer located on a side of the first transparent conductive layer away from the color-changing layer, and through holes are provided in the first transparent conductive layer, the color-changing layer and the second transparent conductive layer to form the first blind hole.

[0028] That is, a through hole is opened in the three-layer electrochromic device, while the first transparent protective layer is not opened to form a blind hole. The part that needs to receive the incident light (such as the camera or the protruding camera) will not be blocked or covered by the color-changing layer, so that the incident light can be unobstructed. When the protruding part is a camera, it will not affect the use of the camera.

[0029] Preferably, if Figure 3 As shown, the electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer, the first transparent conductive layer, the color-changing layer and the second transparent conductive layer have a second through hole, the first transparent protective layer has a second blind hole, and the second through hole and the second blind hole form the first blind hole.

[0030] When the total thickness of the first transparent conductive layer, the color-changing layer and the second transparent conductive layer is less than the height of the protruding part of the electronic terminal device, a second blind hole needs to be provided on the first transparent protective layer, corresponding to the second through hole formed by the first transparent conductive layer, the color-changing layer and the second transparent conductive layer, to form a first blind hole that can accommodate the protruding part of the electronic terminal device; that is, the total height of the second through hole and the second blind hole needs to be greater than or equal to the height of the protruding part of the electronic terminal device.

[0031] In order to ensure that the color changing effect of the electrochromic device in the protruding part or other functional area of ​​the electronic terminal device is consistent with the electrochromic effect of other parts, the present invention can also set the area corresponding to the protruding part or other functional area of ​​the electronic terminal device with an electrochromic device (the second electrochromic device or the third electrochromic device mentioned below). If the functional area of ​​the electronic terminal device is a camera, it is only necessary to make this area transparent when taking pictures, and when not taking pictures, the color changing effect of this area is consistent with that of other parts.

[0032] There are several specific implementation methods:

[0033] Preferably, if Figure 4 As shown, the electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer, and a third through hole is provided in the first transparent conductive layer, the color-changing layer and the second transparent conductive layer to form the first blind hole. A second electrochromic device is provided at the bottom of the first blind hole, and the thickness of the second electrochromic device is less than or equal to the total thickness of the first transparent conductive layer, the color-changing layer and the second transparent conductive layer.

[0034] The second electrochromic device includes a third transparent conductive layer, a second color-changing layer and a fourth transparent conductive layer.

[0035] The second electrochromic device can be made of the same materials as the electrochromic device described in the first aspect of the present invention, with the difference being that the thickness of one or more layers is modified. The second electrochromic device of the present invention includes a third transparent conductive layer, a second color-changing layer, and a fourth transparent conductive layer. In a specific implementation, the thickness of the conductive layer or the color-changing layer, or the thickness of one or more layers of the electrochromic material layer, electrolyte layer, and ion storage layer included in the color-changing layer, can be modified. In short, ensuring that the height of the finally formed first blind hole matches the height of the protruding portion of the electronic terminal device can meet the application requirements.

[0036] When the thickness of the second electrochromic device is equal to the total thickness of the first transparent conductive layer, the color-changing layer and the second transparent conductive layer, it can be applied to an electronic terminal device similar to a flat camera. When taking a picture is required, the second electrochromic device becomes transparent to allow incident light to enter.

[0037] Preferably, if Figure 5 As shown, the electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer and a second transparent protective layer located on the side of the second transparent conductive layer away from the color-changing layer. The second transparent protective layer is provided with a fourth blind hole or a fourth through hole to form the first blind hole.

[0038] When the thickness of the second protective layer is relatively thick, blind holes or through holes may be provided on the second transparent protective layer to meet the height requirement of the protruding portion of the electronic terminal device.

[0039] Preferably, if Figure 6 As shown, the electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer and a second transparent protective layer located on the side of the second transparent conductive layer away from the color-changing layer. A fifth through hole is provided in the first transparent conductive layer, the color-changing layer, the second transparent conductive layer and the second transparent protective layer to form the first blind hole. A third electrochromic device is provided at the bottom of the first blind hole. The thickness of the third electrochromic device is less than or equal to the total thickness of the first transparent conductive layer, the color-changing layer, the second transparent conductive layer and the second transparent protective layer.

[0040] The third electrochromic device includes a fifth transparent conductive layer, a third color-changing layer, a sixth transparent conductive layer and a third transparent protective layer, and the third transparent protective layer is located on a side away from the first transparent protective layer.

[0041] Regardless of whether a protective layer is set or not, it is only necessary to ensure that the size of the blind hole set on the electrochromic device can meet the use requirements and the height can meet the height requirements of the protruding part of the electronic terminal equipment. The material of the electrochromic device set in the blind hole part can be consistent with other parts, and the thickness of one or several layers can be adaptively reduced to meet the requirements.

[0042] Preferably, a cover plate is further included, and the cover plate is located on a side of the first protective layer away from the color-changing layer.

[0043] When the electrochromic device is used as a mobile phone back cover or a mobile phone protective cover, a cover plate can be provided to further protect the electrochromic device provided by the present invention.

[0044] Preferably, the cover plate includes a third curved portion and a fourth curved portion, the third curved portion covers the first curved portion, and the fourth curved portion covers the second curved portion.

[0045] Preferably, the cover plate further includes a main body portion, and the main body portion covers the first conductive portion.

[0046] Preferably, the main body is made of a transparent material, including but not limited to any one or a combination of at least two of polymethyl methacrylate, polycarbonate, polyurethane, polyisocyanate, polyethylene terephthalate or glass.

[0047] Preferably, the third curved portion and the fourth curved portion are both made of non-transparent materials, and are independently selected from any one or a combination of at least two of ABS plastic, polypropylene or silicone, including but not limited to the above materials.

[0048] In order to achieve the electrochromic effect without affecting the aesthetics, the main body of the cover is designed to be made of transparent material so as not to affect the color-changing effect; while the curved part is designed to be made of non-transparent material to hide the internal wiring or external circuits.

[0049] Preferably, a reflective film is further included, and the reflective film is arranged on a side of the second transparent conductive layer away from the color-changing layer.

[0050] When the color-changing layer becomes transparent, the electrochromic device provided by the present invention has the function of a mirror, achieving multiple goals at one stroke.

[0051] Preferably, the color-changing layer of the electrochromic device has a designed pattern.

[0052] Arranging a pattern on the color-changing layer of the present invention can realize the pattern-changing function of the electrochromic device of the present invention. The present invention does not impose too many restrictions on the method of setting the pattern. For example, photolithography technology can be used.

[0053] In the present invention, the present invention does not overly limit the thickness range of each layer. As long as the thickness range of the application can be adopted, for example, the thickness of the conductive layer can be 5-1000nm, such as 10nm, 50nm, 100nm, 200nm, 400nm, 500nm, 600nm, 800nm, 900nm, etc., preferably 20-50nm. The thickness of the electrochromic material layer can be 5-1000nm, such as 10nm, 50nm, 100nm, 200nm, 400nm, 500nm, 600nm, 800nm, 900nm, etc., preferably 150-300nm. The thickness of the ion storage layer can be 5-1000nm, such as 10nm, 50nm, 100nm, 200nm, 400nm, 500nm, 600nm, 800nm, 900nm, etc., preferably 150-300nm. The thickness of the electrolyte layer may be 0.01-100 μm, for example, 0.1 μm, 1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 70 μm, 80 μm, 90 μm, etc., preferably 2-25 μm. The thickness of the protective layer may be 1-1000 μm, for example, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 200 μm, 500 μm, 800 μm, etc.

[0054] As long as the constituent materials that meet the application requirements of the present invention are used to form different structural layers, they can be applied to the present invention. The present invention does not specifically limit the thickness of each layer, as long as they can meet the application requirements, they can be adopted.

[0055] Preferably, the components of the first conductive layer and the second conductive layer independently include any one or a combination of at least two of indium tin oxide (ITO), aluminum zinc oxide (AZO), fluorine-doped tin oxide (FTO), silver nanowires, graphene, carbon nanotubes, metal mesh transparent conductive electrodes or nano silver paste.

[0056] Preferably, the first transparent substrate and the second transparent substrate are each independently made of glass or a flexible substrate material, and the flexible material includes but is not limited to polyethylene terephthalate, cyclic olefin copolymer, and triacetate cellulose.

[0057] Preferably, the ion storage layer comprises any one or a combination of at least two oxides or complexes formed by metal elements from the seven subgroups and Group VIII (referring to Groups IIIB, IVB, VB, VIB, VIIB, VIII, IB, and IIB) that can store ions during electrochemical reactions. The term "metal oxide" refers to a metal oxide, a combination of two or more metal oxides, a metal complex, a combination of two or more metal complexes, or a combination of a metal complex and a metal oxide.

[0058] If two or more metal oxides are selected, it refers to a doped form, for example, Nb2O5 doped with 5wt% TiO2.

[0059] Preferably, the metal includes any one of titanium (Ti), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), iridium (Ir), nickel (Ni), copper (Cu), and zinc (Zn), or a combination of at least two of them.

[0060] Preferably, the complex is selected from transition metal complexes such as Prussian green, Prussian white, Prussian brown or sky blue Fe4[Fe(CN)6]3, ferrous oxide, ferric oxide, ferrosoferric oxide, KFeFe(CN)6, FeNiHCF, FeHCF, NiHCF, Prussian blue nanoparticles or N x M y {Fe(CN)6} (M represents a metal element, including iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), zinc (Zn), copper (Cu), etc.; N represents an alkali metal ion, such as Na, K and other alkali metals).

[0061] Preferably, the composition of the ion storage layer further includes a redox active polymer.

[0062] In the present invention, the ion storage layer can be a mixed system of a transition metal complex and a metal oxide, a mixed system of a transition metal complex and a polymer having redox activity, or a mixed system of a metal oxide and a polymer having redox activity.

[0063] The redox-active polymers include polymers formed of pyrrole and pyrrole derivatives, polymers formed of thiophene and thiophene derivatives, polymers containing TEMPO (tetramethylpiperidinium N-oxide) and its derivatives, polymers containing viologen and its derivatives, and the like.

[0064] The redox-active polymer may include, but is not limited to, redox-active nitrooxy or semi-vinyl radical polymers, such as poly(nitrostyrene), poly(propylenedioxystyrene), conjugated polymers (including polyaniline, PEDOT:PSS, polypyrrole, etc.).

[0065] Preferably, the components of the electrochromic material layer include colored metal oxides, polydecyl viologen and its derivatives, benzyl viologen polymer (poly(decylviologen)) and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly(3,4-ethylenedioxythiophene) and its derivatives, poly(propylenedioxythiophene) and its derivatives, polyisofluorene (polyfurane) and its derivatives, polythiophene and [3,4-b Any one or a combination of any two of ][1,4]dioxepane and its derivatives, polyfuran and its derivatives, polyfluorene and its derivatives or polycarbazole and its derivatives, and / or a copolymer formed by a monomer or oligomer of the above polymers and an electron-deficient monomer; the above polymer refers to polydecyl viologen and its derivatives, benzyl viologen polymer and its derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly3,4-ethylenedioxythiophene and its derivatives, polypropylenedioxythiophene and its derivatives, polyisofluorene and its derivatives, polythieno[3,4-b][1,4]dioxepane and its derivatives, polyfuran and its derivatives, polyfluorene and its derivatives or polycarbazole and its derivatives.

[0066] Preferably, the electron-deficient monomer includes any one of benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzoimidazole, quinoxalines or diketopyrrolopyrroles, or a combination of at least two thereof.

[0067] Preferably, the electrolyte layer is selected from a gel electrolyte layer, a liquid electrolyte layer or a solid electrolyte layer, more preferably a solid electrolyte layer, and even more preferably a solid flexible electrolyte layer.

[0068] The flexibility mentioned in the present invention means that the material has a certain degree of flexibility, and the material can be bent, stretched, twisted, etc., and its physical and chemical properties will not change during and after deformation.

[0069] In the current prior art, gel electrolytes or liquid electrolytes are generally selected because they can easily obtain higher ionic conductivity. However, gel electrolytes or liquid electrolytes have a short service life and poor stability, and cannot be applied to large-scale devices. Therefore, the present invention specifically prefers solid electrolytes, which have better stability, safety and good processability.

[0070] Since electrochromic devices require high transparency, traditional solid electrolytes are generally not applicable, except for inorganic solid electrolytes such as lithium phosphorus oxynitride (Lipon), but its ionic conductivity is too low and can only be processed by high vacuum sputtering, or solid electrolytes made by mixing polymers with plasticizers. For example, polyethylene oxide (PEO) is blended with succinonitrile and lithium salt to obtain a solid electrolyte with higher conductivity. However, the small molecule plasticizers in conventional solid electrolyte materials can easily penetrate into the color-changing layer and damage the device.

[0071] The preferred solid flexible electrolyte layer of the present invention has high transparency, good ionic conductivity (>10 -6 S / cm) and the beneficial effects of high stability,

[0072] Preferably, the weight percentage of the neutral organic small molecules contained in the solid flexible electrolyte layer is ≤30wt%, for example, 25wt%, 20wt%, 15wt%, 10wt%, 5wt%, etc., and the molecular weight of the neutral organic small molecules is ≤3000, for example, 2500, 2000, 1500, 1000, 500, etc.

[0073] Preferably, the components of the solid electrolyte layer include a solid electrolyte polymer having plasticizing groups connected by covalent bonds.

[0074] Preferably, the components of the solid electrolyte layer include a copolymer of a monomer or oligomer and an ion-conductive polymer, and the side chain of the monomer or oligomer has a plasticizing group. Further preferably, the components of the solid electrolyte layer also include a monomer or oligomer fragment with a cross-linking group on the side chain.

[0075] The "further preferably" mentioned in the present invention means that, in the above definition, the components of the solid electrolyte layer, on the premise that the components include a copolymer of a monomer or oligomer and an ion-conductive polymer, preferably the components of the solid electrolyte layer also include a monomer or oligomer fragment having a cross-linking group in the side chain; the same explanation shall be given to the "further preferably" mentioned below.

[0076] The plasticizing group and plasticizing group refer to groups that can weaken the interaction between polymers and reduce the crystallinity of polymers.

[0077] Preferably, the components of the solid electrolyte layer include a plasticized linear polymer and an ion conductive polymer, which are chemically bonded. The plasticized linear polymer has a glass transition temperature lower than -20°C, for example, -21°C, -22°C, -23°C, -25°C, -28°C, -30°C, -32°C, -35°C, -40°C, etc. Further preferably, the components of the solid electrolyte layer also include a monomer or polymer having a cross-linking group on the side chain, and the monomer or polymer having a cross-linking group on the side chain is chemically bonded to the plasticized linear polymer and the ion conductive polymer.

[0078] Preferably, the components of the solid electrolyte layer include a polymer having a plasticizing group on the side chain and a glass transition temperature below -20°C and an ion-conductive polymer, and the two are connected by chemical bonds. Further preferably, the components of the solid electrolyte layer also include a monomer or polymer having a cross-linking group on the side chain, and the monomer or polymer having a cross-linking group on the side chain, the polymer having a plasticizing group on the side chain and a glass transition temperature below -20°C and the ion-conductive polymer are chemically bonded.

[0079] Preferably, the components of the solid electrolyte layer include brush polymers, which have a flexible polymer main chain, ion-conductive side chains and non-mixable side chains. Further preferably, the components of the solid electrolyte layer also include monomers or oligomers with cross-linking groups on the side chains, and the monomers or oligomers with cross-linking groups on the side chains are chemically bonded to the brush polymer in the form of block copolymers.

[0080] The non-mixable side chains described in the present invention refer to side chains that have significantly different properties from other side chains or polymers and cannot be effectively blended. The brush polymers provided by the present invention refer to polymers whose main chains are flexible polymers with two types of side chains: one type of side chain is used for ion conduction, and the other type of side chain is a type of side chain that has significantly different properties from the ion-conducting side chains and cannot be effectively blended. The introduction of such non-mixable side chains in the present invention can reduce the crystallinity of the polymer, making the polymer in a random state, thereby improving the overall ion-conducting ability and transparency of the polymer.

[0081] In the present invention, the raw materials for preparing the solid flexible electrolyte layer include all-solid polymer electrolyte materials that basically come from the following four categories of polymers.

[0082] wherein x, y, and z are each independently selected from integers greater than 0. The rectangles shown in the figure represent polymer blocks with ion-conducting properties (ion-conducting polymer blocks), and the ovals represent monomers or polymers with side chains such as PR (plasticizing group), CL (crosslinking group), NM (immiscible group), or IC (ion-conducting group).

[0083] (1)

[0084] A block copolymer (represented by PEGPRCL) is formed by copolymerizing a polymer block y having an ion-conducting effect (such as polyethylene glycol or other materials reported in the literature) with a monomer or polymer block x having a plasticizing group (PR) on the side chain, and a monomer or polymer block z having a cross-linking group (CL) on the side chain. Alternatively, a block copolymer (represented by PEGPR) is formed by copolymerizing a polymer block y having an ion-conducting effect (such as polyethylene glycol or other materials reported in the literature) with a monomer or polymer block x having a plasticizing group (PR) on the side chain.

[0085] (2)

[0086] A block copolymer (denoted as PEGSPCL) formed by copolymerizing an ion-conducting polymer block y (such as polyethylene glycol or other materials reported in the literature) with a linear plasticizing polymer (SP) block x (such as polyethylene, polybutylene, polyisobutylene, siloxane, or other materials reported in the literature) having a glass transition temperature below -20°C, and a monomer or polymer block z having a crosslinking group (CL) on its side chain. Alternatively, a block copolymer (denoted as PEGSP) formed by chemically linking an ion-conducting polymer block y (such as polyethylene glycol or other materials reported in the literature) with a linear plasticizing polymer (SP) block x (such as polyethylene, polybutylene, polyisobutylene, siloxane, or other materials reported in the literature) having a glass transition temperature below -20°C.

[0087] (3)

[0088] A block copolymer (represented as PEGSP-PRCL) is formed by chemically linking an ion-conducting polymer block y (such as polyethylene glycol or other materials reported in the literature) with a plasticizing polymer (SP-PR) block x having plasticizing side chains, and then copolymerizing with a monomer or oligomer (CL) block z having crosslinking groups on its side chains. Alternatively, a block copolymer (represented as PEGSP-PR) is formed by chemically linking an ion-conducting polymer block y (such as polyethylene glycol or other materials reported in the literature) with a plasticizing polymer (SP-PR) block x having plasticizing side chains.

[0089] (4)

[0090] A comb-shaped block copolymer (ICNMCL) is formed by chemically linking a flexible polymer block x with an ion-conducting oligomer or polymer (such as polyethylene glycol or other materials reported in the literature) as a side chain and a flexible polymer block y with side chains that are incompatible with the ion-conducting polymer (such as alkyl, aromatic, or alkyl and aromatic mixed side chains), and then copolymerizing with a monomer or oligomer (CL) block z with cross-linking groups on the side chain. Alternatively, a comb-shaped block copolymer (ICNM) is formed by chemically linking a flexible polymer block x with an ion-conducting oligomer or polymer (such as polyethylene glycol or other materials reported in the literature) as a side chain and a flexible polymer block y with side chains that are incompatible with the ion-conducting polymer (such as alkyl, aromatic, or alkyl and aromatic mixed side chains).

[0091] The polymer materials used in the electrolyte layer need to be blended with a certain amount of organic and inorganic salts to form electrolyte precursors. Inorganic salts include but are not limited to cations such as Li + 、Na + , K + Mg 2+ , Ca 2+ 、Al 3+ Inorganic salts, organic salts include but are not limited to ionic liquids, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMIOTf), etc. Sometimes, an initiator is also required to blend to form an electrolyte precursor, which is cross-linked by heating, photoinitiation, etc. to form the final all-solid-state electrolyte.

[0092] In the present invention, for easier understanding, the above four types of polymers are exemplified as follows:

[0093] Polymer A, a solid electrolyte polymer of PEGPRCL in (1), is prepared as follows:

[0094]

[0095] A suitable organic solvent is prepared by adding PEG (polyethylene glycol) capped with bromoisobutyric acid, an acrylate with a plasticizing group, a crosslinking group with two acrylic acids, a monovalent copper catalyst, and a PMDETA (N,N,N',N",N"-pentamethyldiethylenetriamine) ligand. The mixed solution is reacted at 50-130°C for 1-48 hours, filtered through diatomaceous earth, and the solvent is removed under reduced pressure to obtain a polymer solid electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device fabrication.

[0096] Polymer B, a solid electrolyte polymer of PEGPR in (1), is prepared as follows:

[0097]

[0098] PEG diamine (polyethylene glycol diamine) and phthaloyl chloride are added to a suitable organic solvent and directly polymerized under alkaline conditions. After washing, separation, drying, and solvent removal, a polymer electrolyte is obtained. This mixture without solvent can also be used as an electrolyte precursor directly for device preparation.

[0099] The polymer C is a solid electrolyte polymer of PEGSPCL in (2), and the preparation method is as follows:

[0100]

[0101] PEG (polyethylene glycol), polysiloxane diamine, a crosslinking agent tetramine, and a condensing agent CDI (carbonyl diimidazole) are added to a suitable organic solvent; the mixture is reacted at 10-130°C, washed with water, separated, dried, and the solvent removed to obtain a polymer electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device fabrication.

[0102] The polymer D is a solid electrolyte polymer of PEGSP in (2), and is prepared as follows:

[0103]

[0104] PEG (polyethylene glycol), polysiloxane diamine, and the condensing agent CDI (carbonyl diimidazole) are added to a suitable organic solvent and reacted at 10-130°C. The mixture is then washed with water, separated, dried, and the solvent removed to obtain a polymer electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device preparation.

[0105] The polymer E, a solid electrolyte polymer belonging to (3)PEGSP-PRCL, is prepared as follows:

[0106]

[0107]

[0108] PEG (polyethylene glycol), polysiloxane diol, a crosslinking agent tetraol, and a condensing agent CDI (carbonyl diimidazole) are added to a suitable organic solvent and reacted at 10-130°C. The mixture is then washed with water, separated, dried, and the solvent removed to obtain a polymer electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device preparation.

[0109] The polymer F is a solid electrolyte polymer of PEGSP-PR in (3), and is prepared as follows:

[0110]

[0111] PEG (polyethylene glycol), polysiloxane diol, and a condensing agent, carbonyl diimidazole (CDI), are added to a suitable organic solvent and reacted at 10-130°C. The mixture is then washed with water, separated, dried, and the solvent removed to obtain a polymer electrolyte. This mixture, without the addition of a solvent, can also be used directly as an electrolyte precursor for device fabrication.

[0112] The polymer G, a solid electrolyte polymer belonging to ICNMCL in (4), is prepared as follows:

[0113]

[0114] Alkyl acrylate, polyethylene glycol acrylate, ethylene glycol diacrylate, and AIBN (azobisisobutyl cyanide) are added to a suitable organic solvent and reacted under light or heat. The mixture is then washed, separated, dried, and the solvent removed to produce a polymer electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device fabrication.

[0115] The polymer H, a solid electrolyte polymer belonging to the ICNM in (4), is prepared as follows:

[0116]

[0117] Alkyl acrylate, polyethylene glycol acrylate, and AIBN (azobisisobutyl cyanide) are added to a suitable organic solvent. After light exposure or heating, the mixture is washed with water, separated, dried, and the solvent removed to obtain a polymer electrolyte. This mixture, without the addition of solvent, can also be used directly as an electrolyte precursor for device fabrication.

[0118] When the present invention utilizes the four types of polymers (1)-(4), specifically, polymer AH, to prepare an all-solid-state flexible electrolyte layer, it needs to be mixed with an organic inorganic salt and then cross-linked. For example, the polymer is mixed with a lithium salt and a UV curing initiator in a mass ratio of 45:45:10. After magnetic stirring for 30 minutes, the mixture is degassed using ultrasonic vibration for 30 minutes to obtain a precursor solution. The precursor solution can be coated by coating or the like to obtain a solid flexible electrolyte layer.

[0119] The protective layer used in the present invention can be made of a transparent material to meet the application requirements. In order to facilitate bending to obtain the curved portion, a flexible transparent material is preferably used. Any transparent flexible material that can meet the application requirements can be used, such as polyethylene terephthalate, cyclic olefin copolymer, triacetate cellulose, etc.

[0120] In the present invention, each layer is preferably a flexible solid-state layer, and in particular, the electrolyte layer is a flexible all-solid-state electrolyte layer. Thus, the resulting electrochromic device is a flexible all-solid-state electrochromic device, which has an extremely wide range of applications. It can be applied to both planar structures and curved or folded structures. Even after bending or folding, it still maintains excellent performance and can achieve an integrated color-changing effect. The flexible all-solid-state device provided by the present invention has the advantages of a wide range of applications, high stability, and ease of processing.

[0121] In a third aspect, the present invention provides a use of the electrochromic device according to the first aspect in a front display screen, a rear cover or a protective cover of an electronic terminal device.

[0122] Preferably, the electronic terminal device includes a mobile phone, a tablet computer, a laptop computer, a desktop computer, a television, a camera, a microscope, an LED display screen or an OLED display screen.

[0123] Preferably, the protective shell is used to protect electronic terminal equipment, including a mobile phone shell or a tablet computer protective shell.

[0124] Compared with the prior art, the present invention has the following beneficial effects:

[0125] (1) When the electrochromic device provided by the present invention is used, the film body can be attached to the back panel of an electronic terminal device as the main body, or can be used as a display screen of the electronic terminal device, while the first curved portion and the second curved portion are attached to the frame of the electronic terminal device, thereby achieving an integrated electrochromic effect.

[0126] (2) The electrochromic device provided by the present invention can be used as a display screen, and can also be matched with electronic terminal equipment with special functional areas (such as cameras or fingerprint collection functions). Regardless of whether the special functional areas are flat designs, they can meet application requirements.

[0127] (3) The present invention preferably provides a flexible all-solid-state electrochromic device, wherein each layer structure included therein is a flexible solid-state structure, and the electrolyte layer is also preferably a flexible solid-state electrolyte layer; the flexible all-solid-state electrochromic device can be applied to both planar structures and bendable and foldable structures. BRIEF DESCRIPTION OF THE DRAWINGS

[0128] Figure 1 It is a structural diagram of setting through holes.

[0129] Figure 2 This is a schematic diagram of the structure of setting blind holes Figure 1 .

[0130] Figure 3 This is a schematic diagram of the structure of setting blind holes Figure 2 .

[0131] Figure 4 This is a schematic diagram of the structure of setting blind holes Figure 3 , wherein a second electrochromic device is provided in the blind hole.

[0132] Figure 5 This is a schematic diagram of the structure of setting blind holes Figure 4 .

[0133] Figure 6 This is a schematic diagram of the structure of setting blind holes Figure 5 , wherein a third electrochromic device is provided in the blind hole.

[0134] Figure 7 This is a schematic diagram of the morphology and structure of the electrochromic device provided in Example 1 of the present invention.

[0135] Figure 8 Schematic diagram of the interlayer structure distribution of the electrochromic device provided in Example 1 of the present invention.

[0136] Figure 9 This is a schematic diagram of the morphology and structure of the electrochromic device provided in Example 2 of the present invention.

[0137] Figure 10 Schematic diagram of the interlayer structure distribution of the electrochromic device provided in Example 3 of the present invention.

[0138] Figure 11 Schematic diagram of the interlayer structure distribution of the electrochromic device provided in Example 4 of the present invention.

[0139] Among them, 1-thin film main body; 11-first protective layer; 12-first transparent conductive layer; 1201-third transparent conductive layer; 1202-fifth transparent conductive layer; 13-color-changing layer; 1301-second color-changing layer; 1302-third color-changing layer; 131-electrochromic material layer; 132-electrolyte layer; 133-ion storage layer; 14-second transparent conductive layer; 1401-fourth transparent conductive layer; 1402-sixth transparent conductive layer; 15-second transparent protective layer; 1502-third transparent protective layer; 2-first bending portion; 3-second bending portion; 4-electrode lead; 5-through hole.

[0140] Figure 12 This is a structural schematic diagram of a mobile phone with electrochromic function provided in Application Example 1 of the present invention.

[0141] Among them, 10 is the mobile phone body; 20 is the electrochromic device; 30 is the back cover; 301 is the circuit board. DETAILED DESCRIPTION

[0142] The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0143] It should be noted that, in the main body of the film, the first transparent protective layer is also referred to as the first protective part, the first transparent conductive layer is also referred to as the first conductive part, the second transparent protective layer is referred to as the third protective part, and the second transparent conductive layer is referred to as the third conductive part. For the following embodiments and application examples, in order to avoid confusion due to too many numbers, the main body of the film is not specifically written as the first protective part, the first conductive part, etc.

[0144] In the following embodiments, although specific thickness ranges of each layer are given, in fact, in the present invention, those skilled in the art can adjust according to actual conditions, and all of them should be included in the protection scope of the present invention.

[0145] Example 1

[0146] An electrochromic device, such as Figure 7 As shown, it includes a film main body portion 1, a first bent portion 2 and a second bent portion 3.

[0147] The first curved portion 2 and the second curved portion 3 are respectively located on the left and right sides of the film main body (ie, the left and right frames).

[0148] Among them, such as Figure 8 As shown, the electrochromic device is composed of a first transparent conductive layer 12, a color-changing layer 13 and a second transparent conductive layer 14 in sequence.

[0149] The color-changing layer 13 is composed of an electrochromic material layer 131 , an electrolyte layer 132 and an ion storage layer 133 .

[0150] Among them, the first transparent conductive layer 12 includes a first conductive part and a second conductive part, the second transparent conductive layer 14 includes a third conductive part and a fourth conductive part, the color-changing layer 13 is located between the first conductive part and the third conductive part, and the first conductive part, the color-changing layer and the third conductive part together form the film main body 1, the second conductive part is bent to form a first bent part 2, and the fourth conductive part is bent to form a second bent part 3.

[0151] The first bending portion and the second bending portion are respectively provided with electrode leads 4 .

[0152] The first transparent conductive layer 12 is composed of an indium tin oxide layer (30 nm thick) and a polyethylene terephthalate (PET) layer, and is purchased from Jiangsu Rijiu Optoelectronics with a serial number of I100-SE125-P1.

[0153] The electrochromic material layer 131 is composed of poly(ethylhexane propylenedioxythiophene) and has a thickness of 200 nm.

[0154] The electrolyte layer 132 is a solid flexible electrolyte layer obtained using polymer A and has a thickness of 18 μm.

[0155] The ion storage layer 133 is composed of Prussian blue and has a thickness of 200 nm.

[0156] The second transparent conductive layer 14 is made of indium tin oxide and has a thickness of 30 nm.

[0157] Examples 1.2-1.8

[0158] The difference from Example 1 is that the constituent material of the electrolyte layer is replaced with polymer BH.

[0159] Example 2

[0160] An electrochromic device, such as Figure 9 As shown, the difference from Example 1 is that the first curved portion 2 and the second curved portion 3 are both located at the lower side of the film body (ie, the lower frame).

[0161] Example 3

[0162] An electrochromic device, such as Figure 10 As shown, the difference from Example 1 is that it includes a first protective layer 11 , and the first protective layer 11 is located on the side of the first transparent conductive layer 12 away from the color-changing layer 13 .

[0163] Among them, the first protective layer 11 includes a first protective part and a second protective part, the first transparent conductive layer 12 includes a first conductive part and a second conductive part; the second transparent conductive layer 14 includes a third conductive part and a fourth conductive part, the color-changing layer 13 is located between the first conductive part and the third conductive part, and the first protective part, the first conductive part, the color-changing layer and the third conductive part together form the film main body 1, the second protective part covers the second conductive part, and the two are bent together to form a first curved part 2, and the fourth conductive part is bent to form a second curved part 3.

[0164] The first protection portion and the second protection portion are both made of polyethylene terephthalate (PET) and have a thickness of 125 μm.

[0165] Example 4

[0166] An electrochromic device, such as Figure 11 As shown, the difference from Example 3 is that a second transparent protective layer 15 is included, and the second transparent protective layer 15 is located on the side of the second transparent conductive layer 14 away from the color-changing layer 13 .

[0167] Among them, the first transparent protective layer 11 includes a first protective part and a second protective part, the first transparent conductive layer 12 includes a first conductive part and a second conductive part; the second transparent protective layer 15 includes a third protective part and a fourth protective part, the second transparent conductive layer 14 includes a third conductive part and a fourth conductive part, the color-changing layer 13 is located between the first conductive part and the third conductive part, and the first protective part, the first conductive part, the color-changing layer, the third conductive part and the third protective part together form the film main body 1, the second protective part covers the second conductive part, and the two are bent together to form a first curved part 2, the fourth protective part covers the fourth conductive part, and the two are bent together to form a second curved part 3.

[0168] The second transparent protective layer is made of PET and has a thickness of 125 μm.

[0169] Example 5

[0170] An electrochromic device, which differs from Example 1 in that: Figure 1 As shown, the film main body 1 has a through hole 5 .

[0171] Example 6

[0172] An electrochromic device, which differs from embodiment 3 in that the film main body has a through hole.

[0173] Example 7

[0174] An electrochromic device, which differs from Example 3 in that the main body of the film has a blind hole, and the blind hole is arranged as follows:

[0175] like Figure 2 As shown, in the main body of the film, through holes are provided in the first transparent conductive layer 12 , the color-changing layer 13 and the second transparent conductive layer 14 , which together with the first transparent protective layer 11 form blind holes.

[0176] Example 8

[0177] An electrochromic device, which differs from Example 3 in that the main body of the film has a blind hole, and the blind hole is arranged as follows:

[0178] like Figure 3As shown, in the main body of the film, a second through hole is set for the first transparent conductive layer 12, the color-changing layer 13 and the second transparent conductive layer 14, and a second blind hole is set for the first protective layer 11. The second through hole and the second blind hole are correspondingly set to form a blind hole together with the first protective layer 11.

[0179] Example 9

[0180] An electrochromic device, which differs from Example 3 in that the main body of the film has a blind hole, and the blind hole is arranged as follows:

[0181] like Figure 4 As shown, in the main body of the film, through holes are provided in the first transparent conductive layer 12, the color-changing layer 13 and the second transparent conductive layer 14, which together with the first protective layer 11 form blind holes;

[0182] A second electrochromic device is provided at the bottom of the blind hole, and the second electrochromic device includes a third transparent conductive layer 1201 , a second color-changing layer 1301 and a fourth transparent conductive layer 1401 .

[0183] The material and thickness of each layer of the second electrochromic device are the same as those of the electrochromic device provided in Example 3.

[0184] Example 10

[0185] An electrochromic device, which differs from Example 9 in that the second electrochromic device has a different thickness.

[0186] Wherein, the total thickness of the second electrochromic device is reduced; the total thickness of the second electrochromic device can be reduced by reducing the thickness of the third transparent conductive layer, or the thickness of the second color-changing layer, or the thickness of the fourth transparent conductive layer;

[0187] The total thickness of the second electrochromic device can also be reduced by reducing the thickness of the third transparent conductive layer and the second color-changing layer, or reducing the thickness of the second color-changing layer and the fourth transparent conductive layer, or reducing the thickness of the third transparent conductive layer and the fourth transparent conductive layer.

[0188] The total thickness of the second electrochromic device can also be reduced by reducing the thickness of the third transparent conductive layer, the second color-changing layer, and the fourth transparent conductive layer respectively.

[0189] Among them, the reduction in the thickness of the color-changing layer can be achieved by reducing the thickness of the electrochromic material layer, the electrolyte layer or the ion storage layer, or by reducing the thickness of the electrochromic material layer and the electrolyte layer, or reducing the thickness of the electrolyte layer and the ion storage layer, or reducing the thickness of the electrochromic material layer and the ion storage layer, or reducing the thickness of the electrochromic material layer, the electrolyte layer and the ion storage layer.

[0190] Example 11

[0191] An electrochromic device, which is different from Example 10 in that the electrochromic device provided by this embodiment does not include a first protective layer.

[0192] Example 12

[0193] An electrochromic device, which differs from Example 4 in that the main body of the film has a blind hole, and the blind hole is arranged as follows:

[0194] like Figure 5 As described above, in the main body of the film, a through hole is provided in the second transparent protective layer 15 , forming a blind hole together with the first protective layer 11 , the first transparent conductive layer 12 , the color-changing layer 13 and the second transparent conductive layer 14 .

[0195] Example 13

[0196] An electrochromic device, which differs from Example 4 in that the main body of the film has a blind hole, and the blind hole is arranged as follows:

[0197] like Figure 6 As shown, in the main body of the film, through holes are provided in the first transparent conductive layer 12, the color-changing layer 13, the second transparent conductive layer 14 and the second transparent protective layer 15, which together with the first protective layer 11 form blind holes;

[0198] A third electrochromic device is provided at the bottom of the blind hole. The third electrochromic device includes a fifth transparent conductive layer 1202 , a third color-changing layer 1302 , a sixth transparent conductive layer 1402 and a third transparent protective layer 1502 . The third transparent protective layer 1502 is located on a side away from the first protective layer 11 .

[0199] The materials and thicknesses of the layers of the third electrochromic device are the same as those of the electrochromic device provided in Example 4.

[0200] Example 14

[0201] An electrochromic device, which differs from Example 13 in that the thickness of the third electrochromic device is different.

[0202] Wherein, the total thickness of the third electrochromic device is reduced; the total thickness of the third electrochromic device can be reduced by reducing the thickness of the fifth transparent conductive layer, the third color-changing layer, the sixth transparent conductive layer or the third transparent protective layer;

[0203] The total thickness of the third electrochromic device can also be reduced by reducing the thickness of two of the layers respectively.

[0204] The total thickness of the third electrochromic device can also be reduced by reducing the thickness of any of the three layers.

[0205] The total thickness of the third electrochromic device can also be reduced by reducing the thickness of each of the four layers;

[0206] Among them, the color-changing layer includes an electrochromic material layer, an electrolyte layer and an ion storage layer. Therefore, the reduction in the thickness of the color-changing layer can be achieved by reducing the thickness of the electrochromic material layer, the electrolyte layer or the ion storage layer, or by reducing the thickness of any two of the layers, or reducing the thickness of each of the three layers to achieve the reduction in the thickness of the color-changing layer.

[0207] Example 15

[0208] An electrochromic device is different from the embodiment 1 in that the electrochromic device provided by this embodiment further includes a reflective film layer, which is arranged on the side of the second transparent conductive layer away from the color-changing layer.

[0209] Example 16

[0210] An electrochromic device is different from the embodiment 4 in that the electrochromic device provided by this embodiment further includes a reflective film layer, which is arranged between the second transparent conductive layer and the second transparent conductive layer.

[0211] Example 17

[0212] An electrochromic device differs from embodiment 1 in that a cover plate is provided on a side of the first protective layer away from the color-changing layer.

[0213] The cover plate includes a main body, a third curved portion, and a fourth curved portion. The main body covers the first conductive portion, the third curved portion covers the first curved portion, and the fourth curved portion covers the second curved portion.

[0214] The main body is made of transparent polymethyl methacrylate, and the third curved part and the fourth curved part are both made of non-transparent ABS plastic.

[0215] Example 18

[0216] An electrochromic device differs from embodiment 1 in that the electrode lead is electrically connected to the photosensitive element.

[0217] The electrochromic film provided in the embodiment can be used as a part of a mobile phone back cover. Here are illustrative applications:

[0218] Application Example 1

[0219] A mobile phone with electrochromic function, such as Figure 12 As shown, it is composed of a mobile phone body 10, the electrochromic device 20 provided in Example 1 and a rear shell 30, wherein a circuit board 301 is provided on the side frame of the rear shell 30.

[0220] The preparation method is as follows: printing electrodes in the reserved printed electrode area, connecting the electrode leads set at the first bend and the second bend of the electrochromic device 20 to the circuit board 301, and at the same time, attaching the electrochromic device 20 to the back shell, and assembling them together with the mobile phone body to obtain a mobile phone with electrochromic function.

[0221] Application Example 2

[0222] A mobile phone with an electrochromic function is composed of a mobile phone body, the electrochromic device provided in Example 5, and a back cover, wherein a circuit board is provided on the side frame of the mobile phone body, and the back cover also has through holes at positions corresponding to the through holes of the electrochromic device.

[0223] The preparation method is the same as that of Application Example 1.

[0224] Application Example 3

[0225] A mobile phone with an electrochromic function differs from Application Example 2 in that the electrochromic device provided in Example 13 is used, and the third electrochromic device has thin leads connected to a circuit board.

[0226] Application Example 4

[0227] A mobile phone protective case is composed of the electrochromic device provided in Example 1 and a cover plate, wherein a circuit board is arranged on the cover plate.

[0228] The preparation method comprises the following steps: connecting electrode leads provided on the first and second bent parts of the electrochromic device to a circuit board, and bonding the electrochromic device to a cover plate to obtain a mobile phone protective shell.

[0229] Application Example 5

[0230] A mobile phone protective case is composed of the electrochromic device provided in Example 14 and a cover plate, wherein a circuit board is provided on the cover plate, and the cover plate also has a through hole at a position corresponding to the blind hole of the electrochromic device.

[0231] The preparation method comprises the following steps: connecting electrode leads provided on the first and second bent parts of the electrochromic device to a circuit board, and bonding the electrochromic device to a cover plate to obtain a mobile phone protective shell.

[0232] Application Example 6

[0233] A mobile phone protective case is composed of the electrochromic device provided in Example 10 and a cover plate, wherein a circuit board is provided on the cover plate, and a through hole is provided on the cover plate at a position corresponding to the blind hole of the electrochromic device.

[0234] The preparation method is as follows: refer to Application Example 5, except that the second electrochromic device is connected to the circuit board via a thin lead.

[0235] Application Example 7

[0236] A display screen outer layer with an electrochromic function is located outside a liquid crystal display screen and is composed of a mobile phone body, the electrochromic device provided in Example 2, and a cover plate, wherein the circuit board is placed on the side of the display screen close to the mobile phone body.

[0237] Or the LCD could be replaced with organic light-emitting diodes.

[0238] Application Example 8

[0239] A tablet with an electrochromic function is composed of a tablet body, the electrochromic device provided in Example 2, and a back cover, wherein a circuit board is provided on a side frame of the back cover.

[0240] The preparation method refers to Application Example 1.

[0241] The applicant states that while the present invention illustrates the electrochromic device and its applications through the aforementioned embodiments, the present invention is not limited to the aforementioned process steps, nor does it necessarily rely on the aforementioned process steps for implementation. Persons skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. An electrochromic device, characterized in that: It includes a first transparent conductive layer, a color-changing layer and a second transparent conductive layer arranged in sequence; The first transparent conductive layer includes a first conductive portion and a second conductive portion, the second transparent conductive layer includes a third conductive portion and a fourth conductive portion, the color-changing layer is located between the first conductive portion and the third conductive portion, and the five together form a film main body, the second conductive portion is bent to form a first bent portion, and the fourth conductive portion is bent to form a second bent portion; Wherein, the first curved portion and the second curved portion are respectively provided with electrode leads; The first curved portion and the second curved portion are attached to a frame of the electronic terminal device.

2. The electrochromic device according to claim 1, characterized in that The electrochromic device further includes a first protective layer located on a side of the first transparent conductive layer away from the color-changing layer.

3. The electrochromic device according to claim 2, characterized in that The first protective layer is made of transparent material.

4. The electrochromic device according to claim 2, characterized in that The first protection layer includes a first protection portion and a second protection portion, the first protection portion covers the first conductive portion, the second protection portion covers the second conductive portion, and the second protection portion is made of a non-transparent material.

5. The electrochromic device according to claim 2, characterized in that: The electrochromic device further includes a second transparent protective layer located on a side of the second transparent conductive layer away from the color-changing layer.

6. The electrochromic device according to any one of claims 1 to 5, characterized in that: The color-changing layer includes an electrochromic material layer, an electrolyte layer, and an ion storage layer. The electrochromic material layer is located between the first transparent conductive layer and the electrolyte layer.

7. The electrochromic device according to claim 6, characterized in that: The first transparent conductive layer includes a first transparent substrate and a first conductive layer, the second transparent conductive layer includes a second transparent substrate and a second conductive layer, the first conductive layer is located between the first transparent substrate and the color-changing layer, and the second conductive layer is located between the second transparent substrate and the color-changing layer.

8. The electrochromic device according to claim 1, characterized in that The film body is provided with a first blind hole and / or a first through hole.

9. The electrochromic device according to claim 8, characterized in that: The electrochromic device includes a first transparent protective layer located on a side of the first transparent conductive layer away from the color-changing layer. Through holes are formed in the first transparent conductive layer, the color-changing layer, and the second transparent conductive layer to form the first blind hole.

10. The electrochromic device according to claim 9, characterized in that: The electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer, a second through hole is formed in the first transparent conductive layer, the color-changing layer and the second transparent conductive layer, a second blind hole is formed in the first transparent protective layer, and the second through hole and the second blind hole form the first blind hole.

11. The electrochromic device according to claim 9, characterized in that: The electrochromic device includes a first transparent protective layer located on a side of the first transparent conductive layer away from the color-changing layer, a third through hole is formed in the first transparent conductive layer, the color-changing layer, and the second transparent conductive layer to form the first blind hole, a second electrochromic device is disposed at the bottom of the first blind hole, and a thickness of the second electrochromic device is less than or equal to the total thickness of the first transparent conductive layer, the color-changing layer, and the second transparent conductive layer; The second electrochromic device includes a third transparent conductive layer, a second color-changing layer and a fourth transparent conductive layer.

12. The electrochromic device according to claim 9, characterized in that: The electrochromic device includes a first transparent protective layer located on the side of the first transparent conductive layer away from the color-changing layer and a second transparent protective layer located on the side of the second transparent conductive layer away from the color-changing layer. The second transparent protective layer is provided with a fourth blind hole or a fourth through hole to form the first blind hole.

13. The electrochromic device according to claim 9, characterized in that: The electrochromic device includes a first transparent protective layer located on a side of the first transparent conductive layer away from the color-changing layer, and a second transparent protective layer located on a side of the second transparent conductive layer away from the color-changing layer. A fifth through hole is formed in the first transparent conductive layer, the color-changing layer, the second transparent conductive layer, and the second transparent protective layer to form the first blind hole. A third electrochromic device is disposed at the bottom of the first blind hole. The thickness of the third electrochromic device is less than or equal to the total thickness of the first transparent conductive layer, the color-changing layer, the second transparent conductive layer, and the second transparent protective layer. The third electrochromic device includes a fifth transparent conductive layer, a third color-changing layer, a sixth transparent conductive layer and a third transparent protective layer, and the third transparent protective layer is located on a side away from the first transparent protective layer.

14. The electrochromic device according to claim 2, characterized in that: It also includes a cover plate, which is located on a side of the first protective layer away from the color-changing layer.

15. The electrochromic device according to claim 14, characterized in that: The cover plate includes a third curved portion and a fourth curved portion, the third curved portion covers the first curved portion, and the fourth curved portion covers the second curved portion.

16. The electrochromic device according to claim 14, characterized in that The cover plate further includes a main body portion, and the main body portion covers the first conductive portion.

17. The electrochromic device according to claim 16, characterized in that The main body is made of transparent material.

18. The electrochromic device according to claim 15, characterized in that The third curved portion and the fourth curved portion are both made of non-transparent material.

19. The electrochromic device according to claim 1, characterized in that: It also includes a reflective film, which is arranged on a side of the second transparent conductive layer away from the color-changing layer.

20. The electrochromic device according to claim 19, characterized in that The color-changing layer of the electrochromic device has a designed pattern.

21. The electrochromic device according to claim 7, characterized in that The components of the first conductive layer and the second conductive layer independently include any one or a combination of at least two of indium tin oxide, aluminum zinc oxide, fluorine-doped tin oxide, silver nanowires, graphene, carbon nanotubes, metal mesh transparent conductive electrodes or nano silver paste.

22. The electrochromic device according to claim 7, characterized in that The materials of the first transparent substrate and the second transparent substrate are each independently glass or a flexible substrate material.

23. The electrochromic device according to claim 6, characterized in that The components of the ion storage layer include any one or a combination of at least two of oxides or complexes formed by metal elements in seven subgroups and group VIII that store ions during electrochemical reactions.

24. The electrochromic device according to claim 23, characterized in that The metal includes any one or a combination of at least two of titanium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, iridium, nickel, copper or zinc.

25. The electrochromic device according to claim 23, characterized in that The complex is selected from Prussian green, Prussian white, Prussian brown, Prussian blue, KFeFe(CN)6, FeNiHCF, FeHCF, NiHCF or iron compound X m Y n {Fe(CN)6} or a combination of at least two thereof, wherein X is Na + or K + , Y is Fe 3+ 、Co 3+ 、Ni + 、Mn 2+ 、Zn 2+ or Cu 2+ .

26. The electrochromic device according to claim 23, characterized in that The ion storage layer also includes a redox active polymer.

27. The electrochromic device according to claim 6, characterized in that The components of the electrochromic material layer include any one or a combination of any two of colored metal oxides, polydecyl viologen and its derivatives, benzyl viologen polymers and their derivatives, polyaniline and its derivatives, polypyrrole and its derivatives, polythiophene and its derivatives, poly3,4-ethylenedioxythiophene and its derivatives, polypropylenedioxythiophene and its derivatives, polyisofluorene and its derivatives, polythieno[3,4-b][1,4]dioxepane and its derivatives, polyfuran and its derivatives, polyfluorene and its derivatives, or polycarbazole and its derivatives, and / or copolymers formed by monomers or oligomers of the above polymers and electron-deficient monomers.

28. The electrochromic device according to claim 27, characterized in that The electron-deficient monomer includes any one of benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzimidazole, quinoxaline or dione pyrrolopyrrole, or a combination of at least two thereof.

29. The electrochromic device according to claim 6, characterized in that The electrolyte layer is selected from a gel electrolyte layer, a liquid electrolyte layer or a solid electrolyte layer.

30. The electrochromic device according to claim 29, characterized in that The electrolyte layer is a solid electrolyte layer.

31. The electrochromic device according to claim 30, characterized in that The electrolyte layer is a solid flexible electrolyte layer.

32. The electrochromic device according to claim 31, characterized in that The weight percentage of the neutral organic small molecules contained in the solid flexible electrolyte layer is ≤30 wt %, and the molecular weight of the neutral organic small molecules is ≤3000.

33. The electrochromic device according to claim 30, characterized in that The components of the solid electrolyte layer include a solid electrolyte polymer having plasticizing groups connected by covalent bonds.

34. The electrochromic device according to claim 30, characterized in that The components of the solid electrolyte layer include a copolymer of a monomer or oligomer and an ion-conductive polymer, and the side chain of the monomer or oligomer has a plasticizing group.

35. The electrochromic device according to claim 34, characterized in that The components of the solid electrolyte layer also include monomers or oligomer segments with cross-linking groups on their side chains.

36. The electrochromic device according to claim 30, characterized in that The components of the solid electrolyte layer include a plasticized linear polymer and an ion conductive polymer, which are connected by chemical bonds. The glass transition temperature of the plasticized linear polymer is lower than -20°C.

37. The electrochromic device according to claim 36, characterized in that The components of the solid electrolyte layer also include monomers or polymers with cross-linking groups on the side chains, and the monomers or polymers with cross-linking groups on the side chains are chemically bonded to the plasticized linear polymer and the ion conductive polymer.

38. The electrochromic device according to claim 30, characterized in that The components of the solid electrolyte layer include a polymer with a plasticizing group on the side chain and a glass transition temperature lower than -20°C and an ion conductive polymer, and the two are connected by chemical bonds.

39. The electrochromic device according to claim 38, characterized in that The components of the solid electrolyte layer also include monomers or polymers with cross-linking groups on the side chains, and the monomers or polymers with cross-linking groups on the side chains, the polymer with plasticizing groups on the side chains and a glass transition temperature below -20°C, and the ion conductive polymer are chemically bonded.

40. The electrochromic device according to claim 30, characterized in that The solid electrolyte layer comprises a brush polymer having a flexible polymer main chain, ion-conductive side chains and immiscible side chains.

41. The electrochromic device according to claim 40, characterized in that The components of the solid electrolyte layer further include monomers or oligomers having cross-linking groups on the side chains, and the monomers or oligomers having cross-linking groups on the side chains are chemically bonded to the brush polymer in the form of block copolymerization.

42. The electrochromic device according to any one of claims 1 to 5, characterized in that The electrochromic device further includes an electrically connected photosensitive element and / or thermal sensitive element.

43. Use of the electrochromic device according to any one of claims 1 to 42 in a display screen protective film, a rear cover or a protective cover for protecting an electronic terminal device.

44. Use of the electrochromic device according to claim 43 in a display screen protective film, a rear cover or a protective cover for protecting an electronic terminal device, characterized in that: The electronic terminal device includes a mobile phone, a tablet computer, a laptop computer, a desktop computer, a television, a camera, a microscope, an LED display screen or an OLED display screen.

45. Use of the electrochromic device according to claim 43 in a display screen protective film, a rear cover or a protective cover for protecting an electronic terminal device, characterized in that: The protective case includes a mobile phone case or a tablet computer protective case.

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