阅读说明：本技术 固态电致变色器件制备方法、固态电致变色器件及其应用 (Preparation method of solid electrochromic device, solid electrochromic device and application of solid electrochromic device ) 是由 何嘉智 王宏 王朝 黎毓灵 游利焱 周宇 于 2019-09-13 设计创作，主要内容包括：本发明公开了一种电致变色器件及其制备方法,电致变色器件包括第一柔性基底；设置于所述第一柔性基底上的第一透明电极；设置于所述第一透明电极上的电致变色层；设置于所述电致变色层上的固态电解质层,其中所述固态电解质层中,分子量≤3000的中性有机小分子的质量百分含量低于20%；设置于所述固态电解质层上的离子存储层；设置于所述离子存储层上的第二透明电极；设置于所述第二透明电极上的第二柔性基底。(The invention discloses an electrochromic device and a preparation method thereof, wherein the electrochromic device comprises a first flexible substrate; a first transparent electrode disposed on the first flexible substrate; an electrochromic layer disposed on the first transparent electrode; the solid electrolyte layer is arranged on the electrochromic layer, wherein in the solid electrolyte layer, the mass percentage content of neutral organic micromolecules with the molecular weight less than or equal to 3000 is less than 20%; an ion storage layer disposed on the solid electrolyte layer; a second transparent electrode disposed on the ion storage layer; a second flexible substrate disposed on the second transparent electrode.)

1. An electrochromic device, comprising:

a first flexible substrate;

a first transparent electrode disposed on the first flexible substrate;

an electrochromic layer disposed on the first transparent electrode;

the solid electrolyte layer is arranged on the electrochromic layer, wherein in the solid electrolyte layer, the mass percentage content of neutral organic micromolecules with the molecular weight less than or equal to 3000 is less than 20%;

an ion storage layer disposed on the solid electrolyte layer;

a second transparent electrode disposed on the ion storage layer;

a second flexible substrate disposed on the second transparent electrode.

2. The electrochromic device of claim 1, wherein said solid electrolyte layer does not contain neutral organic small molecules.

3. The electrochromic device of claim 1, wherein the first and second flexible substrates comprise polyethylene terephthalate, cyclic olefin copolymer, or cellulose triacetate.

4. The electrochromic device of claim 1, wherein the first and second transparent electrodes are each independently formed from indium tin oxide, aluminum zinc oxide, fluorine doped tin oxide, silver nanowires, graphene, carbon nanotubes, metal mesh transparent conductive electrodes, or silver nanoparticles.

5. The electrochromic device according to claim 1, wherein the material of the ion storage layer comprises a metal oxide formed of one or at least two metal elements of groups 4 to 12, or a mixture of the metal oxides, or the metal oxide doped with any other metal oxide.

6. The electrochromic device of claim 1 wherein said metal oxide comprises an oxide of Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu or Zn.

7. The electrochromic device of claim 1, wherein the material of the ion storage layer comprises a transition metal complex.

8. The electrochromic device of claim 1, wherein the material of the ion storage layer comprises one or at least two redox-active polymers comprising redox-active nitroxide radicals, a california radical polymer, or a conjugated polymer.

9. The electrochromic device according to claim 1, wherein said electrochromic layer is selected from the group consisting of tungsten trioxide, polydecylviologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers comprising one or a combination of at least two of polypyrrole and its derivatives, polythiophene and its derivatives, poly (3,4-ethylenedioxythiophene) and its derivatives, poly (propylenedioxythiophene) and its derivatives, polyfuran and its derivatives, polyfluorene and its derivatives, polycarbazole and its derivatives and its copolymers, or receptor unit-containing copolymers comprising one or a combination of at least two of benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzimidazole, quinoxaline, and pyrrolopyrroledione.

10. The electrochromic device of claim 1 wherein the polymer in the solid electrolyte layer comprises a solid electrolyte polymer having covalently attached plasticizing groups.

11. The electrochromic device according to claim 1, wherein the polymer in the solid electrolyte layer comprises a copolymer of a monomer or oligomer having a plasticizing group at a side chain thereof and an ion-conductive polymer.

12. The electrochromic device of claim 1 wherein said polymer in said solid electrolyte layer comprises a plasticized linear polymer and an ionically conductive polymer covalently linked, said plasticized linear polymer having a glass transition temperature of less than-20 ℃.

13. The electrochromic device according to claim 1, wherein the polymer in said solid electrolyte layer comprises a plasticized polymer having plasticizing groups attached to its side chains and an ion-conducting polymer, both of which are covalently linked.

14. The electrochromic device of claim 1 wherein said solid electrolyte layer comprises a brush polymer having a flexible polymer backbone, ionically conductive side chains, and one or at least two immiscible side chains.

15. A method for preparing an electrochromic device is characterized by comprising the following steps:

covering a first transparent electrode on a first flexible substrate;

applying an electrochromic layer on a first transparent electrode of the first flexible substrate;

covering a second transparent electrode on a second flexible substrate;

coating an ion storage layer on a second transparent electrode of the second flexible substrate;

arranging an electrolyte solution or an electrolyte precursor solution on the surfaces of the electrochromic layer and/or the ion storage layer or between the electrochromic layer and the ion storage layer;

laminating a first flexible substrate and a second flexible substrate such that a predetermined region of one substrate is not covered by the other substrate, the electrolyte solution or electrolyte precursor solution being interposed between the electrochromic layer and the ion storage layer; and

and solidifying the electrolyte solution or the electrolyte precursor solution to form the electrochromic device.

16. The method of claim 15, further comprising:

and removing the material on the surface of the first transparent electrode or the second transparent electrode in the preset area.

17. The method of claim 16, further comprising:

and wiring is carried out on the preset area.

18. The preparation method according to claim 15, wherein the electrolyte solution or the electrolyte precursor solution forms a solid electrolyte layer after being solidified, and the mass percentage of the neutral small organic molecules with the molecular weight of less than or equal to 3000 in the solid electrolyte layer is less than 20%.

19. The method of claim 15, wherein the electrolyte solution or electrolyte precursor solution is cured by pressing, wherein the pressing is performed by pressing the first flexible substrate and the second flexible substrate at a pressure ranging from 30 MP to 500MP and at a temperature ranging above 90 ℃.

20. The method of claim 15, wherein the applying the electrochromic layer on the first flexible substrate or the ion storage layer on the second flexible substrate is selected from the group consisting of spray coating, spin coating, slot extrusion coating, slot coating, roll-to-roll coating, gravure coating, screen printing, transfer coating, and wire-bar coating.

Technical Field

The application relates to a preparation method of a solid-state electrochromic device, the solid-state electrochromic device and application of the solid-state electrochromic device.

Background

Electrochromic devices (ECDs) can be applied to the fields of home furnishing, automobiles and the like to improve use experience, and therefore people pay extensive attention to the ECDs. ECDs can be classified into gel ECDs, liquid ECDs, and solid ECDs according to the state of an electrolyte used. During assembly of gel or liquid electrolyte ECDs, the Working Electrode (WE) and Counter Electrode (CE) need to be separated by a spacer and a cavity formed between them to inject electrolyte into the cavity. The liquid injection port of the cavity is sealed with epoxy resin glue subsequently. To prevent the electrolyte leakage of the liquid or gel ECDs, complicated design of the sealing structure and the edge structure is required. Although the possibility of leakage occurring may be reduced by adding a polymeric thickener (e.g., PVA, PMMA, PVDF-HFP, etc.) to form a gel electrolyte, the total amount of polymeric thickener typically needs to be less than 20 wt.% to maintain suitable ionic conductivity. At this time, most of the electrolyte layer is still in a liquid or gel state, and thus, a mechanical structural stability of the ECDs is hidden.

Compared with liquid/gel ECDs, the solid ECDs have the advantages of better safety, longer service life, suitability for roll-to-roll production and the like, so that the solid ECDs have better application prospects in a plurality of application scenes.

Disclosure of Invention

The application aims to provide a preparation method of a solid-state electrochromic device, the solid-state electrochromic device and application of the solid-state electrochromic device.

In a first aspect, the present application provides an electrochromic device comprising: a first flexible substrate; a first transparent electrode disposed on the first flexible substrate; an electrochromic material layer disposed on the first transparent electrode; the solid electrolyte layer is arranged on the electrochromic material layer, wherein in the solid electrolyte layer, the mass percentage content of neutral organic micromolecules with the molecular weight less than or equal to 3000 is less than 20%; an ion storage layer disposed on the solid electrolyte layer; a second transparent electrode disposed on the ion storage layer; a second flexible substrate disposed on the second transparent electrode.

In some embodiments, the mass percent content of neutral small organic molecules in the solid electrolyte layer is less than 10%; further, the mass percentage of the neutral organic micromolecules in the solid electrolyte layer is lower than 5%; further, the mass percentage of the neutral organic small molecules in the solid electrolyte layer is less than 3%. In some embodiments, the solid electrolyte layer does not contain neutral organic small molecules that can be detected by the instrument.

In some embodiments, the first and second flexible substrates comprise polyethylene terephthalate, cyclic olefin copolymer, cellulose triacetate, or other now or later developed materials.

In some embodiments, the first and second transparent electrodes are each independently formed from indium tin oxide, aluminum zinc oxide, fluorine doped tin oxide, silver nanowires, graphene, carbon nanotubes, metal mesh transparent conductive electrodes, silver nanoparticles, or other now and or later developed substances.

In some embodiments, the material of the ion storage layer includes a metal oxide formed of one or at least two metal elements of groups 4 to 12, the metal oxide being capable of storing cations in a reduction reaction. The metal oxides include, but are not limited to, oxides of Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ir, Ni, Cu and or Zn, or combinations of two or more of the foregoing, or doped with any of the other metal oxides, such as Nb2O5 doped with 5 wt% TiO2, or other now known or later developed suitable materials.

In some embodiments, the material of the ion storage layer comprises a transition metal complex. The transition metal complex includes, but is not limited to, Prussian green, Prussian white, Prussian brown, Prussian blue, ferrous oxide, ferric oxide, ferroferric oxide, KFeFe (CN)6, FeNiHCF, FeHCF, NiHCF, Prussian blue nanoparticles, or NxMy { Fe (CN)₆M represents a metal element including iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), zinc (Zn), copper (Cu), and the like which are known now or developed in the future, and N represents an alkali metal ion). In some embodiments, the material of the ion storage layer comprises one or at least two redox-active polymers comprising redox-active nitroxide radicals, california radical polymers or conjugated polymers. In some embodiments, the ion storage layer includes a composite of any one of a mixed system of a transition metal complex and a metal oxide, a mixed system of a transition metal complex and a redox-active polymer, and a mixed system of a metal oxide and a redox-active polymer.

In some embodiments, the electrochromic layer comprises tungsten trioxide, polydecylviologen and its derivatives, polyaniline and its derivatives, electrochromic conjugated polymers or copolymers containing acceptor units; the electrochromic conjugated polymer comprises one or a combination of at least two of polypyrrole and derivatives thereof, polythiophene and derivatives thereof, poly (3,4-ethylenedioxythiophene) and derivatives thereof, poly (propylenedioxythiophene) and derivatives thereof, polyfuran and derivatives thereof, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof and copolymers thereof; the acceptor unit-containing copolymer includes one or a combination of at least two of benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzimidazole, quinoxaline, and pyrrolopyrroledione, as well as other suitable materials now known or later developed.

In some embodiments, the polymer in the solid electrolyte layer comprises a copolymer of a monomer or oligomer having a plasticizing group at a side chain thereof and an ion conductive polymer. In some embodiments, the polymer in the solid electrolyte layer comprises a plasticized linear polymer and an ionically conductive polymer, both chemically linked, the plasticized linear polymer having a glass transition temperature of less than-20 ℃. In some embodiments, the polymer in the solid electrolyte layer includes a plasticized polymer having a plasticizing group at a side chain and an ion conductive polymer, which are chemically bonded. In some embodiments, the solid state electrolyte layer includes a brush polymer having a flexible polymer backbone, ionically conductive side chains, and one or at least two immiscible side chains. In some embodiments, the addition of a cross-linking group may increase the mechanical modulus of the solid state electrolyte layer.

In a second aspect, the present application provides a method for preparing an electrochromic device, comprising: covering a first transparent electrode on a first flexible substrate; applying an electrochromic layer on a first transparent electrode of the first flexible substrate; covering a second transparent electrode on a second flexible substrate; coating an ion storage layer on a second transparent electrode of the second flexible substrate; arranging an electrolyte solution or an electrolyte precursor solution on the surfaces of the electrochromic layer and/or the ion storage layer or between the electrochromic layer and the ion storage layer; laminating a first flexible substrate and a second flexible substrate such that a predetermined region of one substrate is not covered by the other substrate, the electrolyte solution or electrolyte precursor solution being interposed between the electrochromic layer and the ion storage layer; and solidifying the electrolyte solution or the electrolyte precursor solution to form the electrochromic device.

In some embodiments, the method further comprises removing material on the surface of the first transparent electrode or the second transparent electrode in the preset region. In some embodiments, the method further comprises routing on the preset area.

In some embodiments, the electrolyte solution or the electrolyte precursor solution forms a solid electrolyte layer after solidification, and the mass percentage content of the neutral small organic molecules with the molecular weight less than or equal to 3000 in the solid electrolyte layer is less than 20%. In some embodiments, the electrolyte solution or electrolyte precursor solution is cured by pressing, the pressing curing being to press the first flexible substrate and the second flexible substrate at a pressure range of 30-500MP and a temperature range of higher than 90 ℃. In some embodiments, the electrolyte solution or electrolyte precursor solution is cured (e.g., 1 atmosphere) at room temperature.

In some embodiments, the method of coating the electrochromic layer on the first flexible substrate or the ion storage layer on the second flexible substrate is selected from spray coating, spin coating, nip extrusion coating, slot coating, roll-to-roll coating, dimpled coating, screen printing, transfer coating, wire bar coating, or other now known or later developed methods. Some inorganic materials can also be prepared by sputtering.

Drawings

The claims of the present application set forth particular features of the various embodiments. A better understanding of the technical features and advantages may be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:

fig. 1 is a block diagram of an electrochromic device according to an embodiment of the present disclosure.

Fig. 2 is a flow chart of the preparation of an electrochromic device according to an embodiment of the present application.

Fig. 3A and 3B are schematic views of two lamination structures provided in the embodiments of the present application, in which a local area of one substrate is not covered by another substrate.

Figure 4 is a schematic illustration of a hexagonal electrochromic layer film and an ion storage layer film provided in accordance with one embodiment of the present application.

Fig. 5 is a schematic illustration of a method of coating an electrolyte precursor onto an electrochromic layer film by a wire bar coater as provided by an embodiment of the present application.

Fig. 6 is a schematic diagram of an ion storage layer dislocation overlaid on an electrolyte coated electrochromic layer as provided by one embodiment of the present application.

Fig. 7 is a schematic diagram of circuit connections for an electrochromic device provided by one embodiment of the present application.

Figure 8A is a schematic illustration of a rectangular electrochromic layer film and an ion storage layer film provided in accordance with one embodiment of the present application.

Fig. 8B is a schematic illustration of an ion storage layer as in fig. 8A being misaligned over an electrolyte coated electrochromic layer as in fig. 8A according to an embodiment of the present application.

Fig. 8C is a schematic diagram of circuit connections for an electrochromic device such as that of fig. 8B, as provided by one embodiment of the present application.

Fig. 9 is a schematic view of an embodiment of the present application in which an electrolyte is dropped between an electrochromic layer film and an ion storage layer film, and the electrochromic layer film and the ion storage layer film are laminated by roll pressing.

FIG. 10 is a graph illustrating the change in light transmittance of thin film ECDs curved at different arcs according to one embodiment of the present application.

Fig. 11(a) - (e) are ECDs pictures under various operations provided by an embodiment of the present application.

Fig. 12 is a graph showing a change in transmittance for switching the ECD every 1s according to an embodiment of the present application.

Fig. 13A is an exploded view of a structure of an anti-glare rearview mirror including a solid ECD according to an embodiment of the present application.

Fig. 13B is a sectional view of the anti-glare rear view mirror of fig. 13A.

Fig. 14A and 14B are schematic views of a process for bending a film to manufacture a rearview mirror according to an embodiment of the present application.

Fig. 15 is a schematic process diagram of an apparatus for manufacturing a rearview mirror according to an embodiment of the present application.

Fig. 16A and 16B are schematic structural views of a roller for rolling a film when manufacturing a rearview mirror according to an embodiment of the present application.

FIG. 17 is a schematic view of another process for making a rearview mirror according to one embodiment of the present application.

Fig. 18 is a schematic view of a process for manufacturing a rearview mirror according to an embodiment of the present application.

FIG. 19 is a schematic view of another process for making a rearview mirror according to one embodiment of the present application.

FIG. 20 is a schematic view of another process for making a rearview mirror according to one embodiment of the present disclosure.

Fig. 21 is a schematic process diagram of a sealing step for manufacturing a rearview mirror according to an embodiment of the present disclosure.

Fig. 22A and 22B are schematic process views of a sealing step for manufacturing a rearview mirror according to an embodiment of the present application.

FIG. 23 is a schematic view of another process for preparing a rearview mirror seal according to one embodiment of the present application.

Fig. 24 is a schematic view illustrating a layered structure of a rearview mirror using an ECD according to an embodiment of the present application.

Detailed Description

In the following detailed description, specific details are set forth in order to provide a better understanding of various embodiments of the present application. However, it will be understood by those skilled in the art that the present application may be practiced without these details. In addition, while various specific embodiments are disclosed herein, it will be appreciated that those skilled in the art, upon attaining an understanding of the present disclosure, may make alterations and modifications within the scope of the disclosure, which modifications are to involve equivalent substitutes for any aspect of the invention so as to attain the same results in substantially the same way.

Unless the context requires otherwise, throughout the description and claims of this application, the word "comprise" and variations of the word, such as "comprises" and "comprising," are to be construed in an open, inclusive sense, i.e., as "including but not limited to. Reference throughout this specification to a range of numerical values is intended to be used as a shorthand notation, referring to each separate value falling within the range including the value defining the range individually and each separate value being incorporated into the specification as if it were individually recited. In addition, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

Reference in the specification to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the application. Thus, the appearances of the phrase "in one embodiment" appearing in various places throughout the specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in different embodiments.

The all-solid-state ECDs of the various embodiments of the present application form a high performance transparent solid electrolyte by an in situ photo-or thermal-crosslinking process and bond the solid working and counter electrode films together. The all-solid-state thin film ECD disclosed herein has good flexibility and can be adapted to any curvature or shape. In some embodiments, a solid electrolyte layer (e.g., 5 μm, which is easy and inexpensive to manufacture) may also function as a separator between the ion conductor and the electrode. The ECDs of the present application have a more stable electrolyte electrode interface due to the reduction of neutral organic small molecules (e.g., solution, plasticizer, ionic liquid) and thus have a longer lifetime than liquid/gel ECDs. In some embodiments, the drive voltage required for the ECDs of the present application is small (e.g., 1.5V), which facilitates application of the ECDs to battery powered devices.

The embodiments are described in detail below with reference to the accompanying drawings. Reference is first made to fig. 1. Fig. 1 is a block diagram of an exemplary electrochromic device 100 according to an embodiment of the present application. The electrochromic device 100 includes a first flexible substrate 102, a first transparent electrode 104 disposed on the first flexible substrate 102, an electrochromic layer 106 disposed on the first transparent electrode 104, a solid electrolyte layer 108 disposed on the electrochromic layer 106, an ion storage layer 110 disposed on the solid electrolyte layer 108, a second transparent electrode 112 disposed on the ion storage layer 110, a second flexible substrate 114 disposed on the second transparent electrode 112, and a power supply 116 connected to the first transparent electrode 104 and the second transparent electrode 112. In some embodiments, solid state electrolyte layer 108 comprises neutral small organic molecules having a molecular weight of no greater than 3000, with a mass percentage of no greater than 20%, 10%, 5%, or 3%. In some embodiments, the solid electrolyte layer 108 does not contain small organic molecules therein, which can be detected or measured by known instruments. In some embodiments, the solid electrolyte layer 108 may include some organic counter ions that are not monomeric/oligomeric components, such as lithium salts.

For convenience, in the present application, the combination of the first flexible substrate 102, the first transparent electrode 104, and the electrochromic layer 106 is referred to as a Working Electrode (WE), and the combination of the second flexible substrate 114, the second transparent electrode 112, and the ion storage layer 110 is referred to as a Counter Electrode (CE).

In some embodiments, the first flexible substrate 102 and the second flexible substrate 114 may be transparent substrates. The materials of the first flexible substrate 102 and the second flexible substrate 114 include, but are not limited to, polyethylene terephthalate (polyethylene terephthalate), cyclic olefin copolymer (cyclic olefin copolymer), cellulose triacetate (triacetate cellulose), or other suitable materials now known or later developed. The first flexible substrate 102 and the second flexible substrate 114 allow the ECDs to be bent into a suitable shape for various applications, such as a rear view mirror, a window, an automobile or ship skylight, and the like. The thickness of the first flexible substrate 102 or the second flexible substrate 114 may be 10-1000 μm.

In some embodiments, first transparent electrode 104 and second transparent electrode 112 may be thin film materials. The material of the first transparent electrode 104 and the second transparent electrode 112 includes, but is not limited to, any one 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, and other known or unknown suitable materials. The thickness of the first transparent electrode 104 or the second transparent electrode 112 may be 1-800 nm.

In some embodiments, the composition of the ion storage layer 110 includes a metal oxide to store cations in a reduction reaction, and the metal of the metal oxide may be any one of groups 4 to 12 of the periodic table or a combination of at least two thereof. In some embodiments, the metal oxide comprises titanium (Ti), vanadium (V), niobium (Nb)Oxides of any one of tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), cobalt (Co), iridium (Ir), nickel (Ni), copper (Cu), zinc (Zn), or a combination of two or more of them, or any one of them doped with other metal oxides, for example Nb₂O₅Doped with 5 wt% TiO₂Or other now known or later developed suitable materials.

In some embodiments, the ion storage layer 110 may include a transition metal complex that may undergo a reduction reaction. Exemplary metal complexes include, but are not limited to, for example, Prussian Green, Prussian white, Prussian Brown, Prussian blue, ferrous oxide, ferric oxide, ferroferric oxide, KFeFe (CN)₆FeNiHCF, FeHCF, NiHCF, Prussian blue nanoparticles or NxMy { Fe (CN)₆M represents a metal element including iron (Fe), cobalt (Co), nickel (Ni), manganese (Mn), zinc (Zn), copper (Cu), etc. known now or developed in the future, and N represents an alkali metal ion such as Na, K, etc. known now or developed in the future.

In some embodiments, the composition of the ion storage layer 110 further includes a redox-active polymer that stores cations in a reversible reduction reaction. Exemplary redox-active polymers may include, but are not limited to, redox nitroxides (redox active nitroxyl), galvanoxyradical polymers (e.g., polynitrooxynitrixystyrene), poly (galvanoxystyrene), or conjugated polymers (including polyaniline (polyaniline), PEDOT: PSS, polypyrrole, and the like, known or later developed suitable materials).

In some embodiments, the ion storage layer 110 may be a mixed system of a transition metal complex and a metal oxide, a mixed system of a transition metal complex and a redox-active polymer, a mixed system of a metal oxide and a redox-active polymer, or the like. The thickness of the ion storage layer 110 is 1nm to 10 μm.

In some embodiments, the electrochromic layer 106 may include one or more layers that may be patternedMaterials that reduce/oxidize and store counter ions. The electrochromic layer 106 may comprise tungsten trioxide (WO)₃) Polydecylviologen (poly) and its derivatives, polyaniline (polyanaline) and its derivatives, various electrochromic conjugated polymers or copolymers containing acceptor units; the electrochromic conjugated polymer includes, for example, any one or a combination of any two of polypyrrole (polypyrole) and its derivatives, polythiophene (polythiophene) and its derivatives, poly (3,4-ethylenedioxythiophene) (poly (3,4-ethylenedioxythiophene)) and its derivatives, poly (propylenedioxythiophene) (poly (propylenedioxythiophene)) and its derivatives, polyfuran (polyfurane) and its derivatives, polyfluorene (polyfluorene) and its derivatives, polycarbazole (polycarbazole) and its derivatives; such receptor monomer-containing copolymers include benzothiadiazole (benzothiadiazoles), benzoselenadiazole (benzoselenadiazoles), benzoxazole (benzoxazoles), benzotriazole (benzotriazoles), benzimidazole (benzoimidazoles), quinoxaline (quinoxalines), pyrrolopyrroledione (diketopyrrolopyrroles), and other now known or later developed materials. The thickness of the electrochromic layer 106 may be 1nm-10 μm.

In some embodiments, the thickness of the solid electrolyte layer 108 is 0.1 μm to 1000 μm. In some embodiments, the solid electrolyte layer 108 may be formed from a liquid material that is cured by Ultraviolet (UV) light or thermally, during which the electrolyte changes from a liquid to a solid. The solid electrolyte layer 108 has good ionic conductivity and stability (e.g., during the debubbling process) at high temperatures in excess of 90 c. The use of the solid electrolyte layer 108 in the ECD100 overcomes a series of problems of easy leakage, instability, complex manufacturing process, etc. of a liquid or gel electrolyte, and has advantages in both production process and safety.

For ECDs, suitable solid-state electrolytes need to be transparent and have high ionic conductivity between the ion storage layer and the electrochromic layer. The solid electrolyte disclosed in the present application has high transparency and good ionic conductivity (>10^-6S/cm) and high stability.

Conventional solid-state electrolytes are mainly used for lithium ion batteries. Since high transparency is required for electrochromic devices, solid electrolytes in the conventional sense are generally not suitable. There are two main types of solid electrolytes that can be used in electrochromic devices. The first is an inorganic solid electrolyte such as lithium phosphorus oxynitride (LiPON), but with too low an ionic conductivity (e.g., 10 f)^-7S/cm) and can only be treated by high vacuum sputtering. The second is a solid electrolyte of a polymer mixed with a plasticizer, for example, polyethylene oxide (PEO) blended with succinonitrile and a lithium salt, which can achieve higher conductivity (e.g., 10)^-4S/cm) solid electrolyte. However, small molecule plasticizers in conventional solid electrolyte materials can easily penetrate into the electrochromic layer during use, destroying the device.

The present application also provides a novel solid electrolyte design concept for forming a solid electrolyte suitable for electrochromic devices by covalently attaching plasticizing groups to an ionically conductive polymer. Typical ion-conducting polymers such as PEO tend to crystallize, resulting in a decrease in transparency and ionic conductivity. By introducing a plasticizing group into the ion-conducting polymer, the ordered arrangement of the polymer chains is disturbed to suppress crystallization. Therefore, the transparency and ionic conductivity of the polymer can be greatly improved, thereby obtaining an electrolyte suitable for ECDs. The plasticizing group may be a small molecule group or a soft polymer chain. Since these plasticizing groups are covalently attached to the polymer chains, they cannot penetrate to other layers of the ECDs. The polymer electrolyte has high ionic conductivity, high transparency and good stability.

In some embodiments, the solid electrolyte layer 108 includes an ion conducting polymer block copolymerized with a monomer or oligomer having a plasticizing group on a side chain thereof. In some embodiments, the plasticizing group is a small molecule group attached to a monomer or oligomer side chain, which can be further block copolymerized with an ion conducting polymer to form a solid state electrolyte. For example, the polymer electrolyte of the solid electrolyte layer may include, but is not limited to:

wherein x, y, and z are each an integer greater than 0, and

in some embodiments, the linkage between the various portions of the backbone, the linkage between the backbone and the plasticizing group (PR), and the linkage between the backbone and the crosslinking group (CL) may be any type of organic bond or bonds.

In the present application, the plasticizing group (PR) may include, but is not limited to, the following structure:

any functional compound capable of linking two or more monomers can be used as the crosslinking group (CL), including, but not limited to, the following structures:

in some embodiments, in preparing the polymer, a monomer or oligomer having a pendant plasticizing group is first synthesized and further linked to the ion conducting polymer by a chain end reaction. These plasticizing groups can reduce the crystallinity of the ion-conducting polymer, increase the ionic conductivity, and increase the transparency of the polymer electrolyte. Since the addition of a plasticizing group may also lower the mechanical modulus of the polymer electrolyte, it may also be necessary to introduce a crosslinking group to maintain its mechanical properties. The polymer may contain one or more types of plasticizing groups in the polymer chain.

An exemplary preparation method is as follows. In some embodiments, the polymer is synthesized by ATPR (atom transfer radical polymerization):

a solution of a mixture of capped PEG (polyethylene glycol), carbon-carbon double bond substituted monomer with a plasticizing group, carbon-carbon double bond substituted monomer with a crosslinking group, in a suitable organic solvent was bubbled with nitrogen for 15 minutes, followed by the addition of monovalent copper catalyst and PMDETA (N, N', N "-pentamethyldiethylenetriamine). The solution that has not been polymerized is referred to as an electrolyte precursor solution. The reaction is carried out for 1-48 hours at 50-130 ℃ under the protection of nitrogen atmosphere, the mixed solution after the reaction is viscous, and the organic phase is filtered by diatomite and subjected to reduced pressure rotary evaporation to remove the solvent to obtain a product (polymer electrolyte solution). The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the polymer is synthesized by an esterification reaction:

adding acyl chloride or active ester into alcohol solution at-10 deg.c in proper organic solvent. Then the base is slowly added to the mixture and the mixture is heated to 50-130 ℃ for 1-48h and water is added to the mixture. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the polymer is synthesized by random copolymers:

in reaction (1), the amine solution and the acid chloride are added in a suitable organic solvent at-10 ℃ to 10 ℃. Then, the base is slowly added into the mixture, the mixture is heated to 50-130 ℃ for reaction for 1-48h, and water is added into the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In reaction (2), the alkyne and azide monomers are added to a suitable organic solvent under a nitrogen atmosphere, followed by the addition of a monovalent copper catalyst. The mixed solution reacts for 1 to 48 hours at the temperature of between 10 and 130 ℃, and water is added into the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In reaction (3), an ethanol monomer solution, and triphosgene and a base or CDI (N, N' -carbonyldiimidazole) are added in a suitable organic solvent at-10 ℃ to 10 ℃, and then the mixture is stirred at 10 ℃ to 130 ℃ for 1 to 48 hours, and water is added to the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or mixtures of electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the solid electrolyte layer 108 may comprise an ionically conductive polymer having a glass transition temperature of less than-20 ℃ linked to a plasticized linear polymer by a chemical bond. Exemplary plasticized linear polymers include, but are not limited to, polyethylene, polybutylene, polyisobutylenes, silicones, and the like. By linking the plasticized linear polymer with the ion-conducting polymer, the ionic conductivity and light transmittance of the polymer can be enhanced.

Exemplary polymer electrolytes can include, but are not limited to:

wherein x, y and z are each an integer greater than 0, and

SP is a flexible polymer with a low glass transition temperature (< -20 ℃). The linkage between the main chains, and the linkage between the main chains and CL (cross-linking group) may be any type of organic bond or bonds.

CL (crosslinking group) may include any functional chemical that can be attached to two or more monomers. Exemplary CL groups can include, but are not limited to:

in some embodiments, polyethylene, PEO, and crosslinking groups may be used to synthesize polymers suitable for use in ECD electrolytes. Exemplary reactions may include, but are not limited to:

in the above reaction, a solution comprising ethanol monomer and functionalized polyethylene, and triphosgene and base or CDI (N, N' -carbonyldiimidazole) are added in a suitable organic solvent at-10 deg.C to 10 deg.C, the mixture is stirred at 10 deg.C to 130 deg.C for 1 to 48 hours, and then water is added to the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, polyisobutylene, polyethylene glycol, and crosslinking groups may form a polymer suitable for use in an ECD electrolyte. Exemplary reactions include, but are not limited to:

in the above reaction, a solution comprising an ethanol monomer and functionalized polyisobutylene is added along with triphosgene and a base or CDI (N, N' -carbonyldiimidazole) at a temperature in the range of-10 ℃ to 10 ℃, the mixture is stirred at 10 ℃ to 130 ℃ for 1 to 48 hours, and then water is added to the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the siloxane, PEO, and crosslinking groups can form a polymer suitable for use in an ECD electrolyte. Exemplary reactions include, but are not limited to:

in the above reaction, a solution containing all the starting materials and siloxane, as well as triphosgene and base or CDI or catalyst, is added in a suitable organic solvent at a temperature of-10 deg.C to 10 deg.C. The mixture was stirred at 10-130 ℃ for 1-48h, and then water was added to the mixed solution. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or mixtures of electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the polymer of the ECD electrolyte may be synthesized as follows:

in the above reaction, 3g of polyethylene glycol (molecular weight. about.300), 3g (1mmol) of (3-aminopropyl) terminated polydimethylsiloxane (molecular weight. about.3000), and 0.015g (0.1mmol) of triethylenetetramine were added to 100mL of DCM (dichloromethane). After cooling the solution to 0 ℃, 1.13g (3.8mmol) of triphosgene was slowly added and 2.5g (24.7mmol) of Triethylamine (Triethylamine) was added dropwise. After stirring at 0 ℃ for 2h, the solution was warmed to room temperature and stirring was continued for 18 h. The organic solution was washed by adding 100mL of deionized water to the mixture. The organic phase was collected over MgSO₄After drying, vacuum distillation was carried out to remove the organic phase to obtain a product (polymer A). The yield is 80-100%.

In some embodiments, the polymer of the ECD electrolyte may be synthesized as follows:

in the above reaction, 6g (1mmol) of polyethylene glycol (MW-6000), 3.0g (1mmol) of (3-aminopropyl) terminated polydimethylsiloxane (MW-3000), and 0.015g (0.1mmol) of triethylenetetramine were added to 100mL of DCM (dichloromethane). After cooling the solution to 0 ℃, 0.21g (0.71mmol) of triphosgene was slowly added and 0.47g (4.6mmol) of Triethylamine (Triethylamine) was added dropwise. After stirring at 0 ℃ for 2h, the solution was warmed to room temperature and stirring was continued for 18 h. The organic solution was washed by adding 100mL of deionized water to the mixture. The organic phase was collected, dried over MgSO4, and distilled under vacuum to remove the organic phase to give a product (polymer B (Polymer B)). The yield is 80-100%.

In some embodiments, the polymer of the ECD electrolyte may be synthesized as follows:

in the above reaction, 6g (1mmol) of polyethylene glycol (MW. about.6000) and 3.0g (1mmol) of (3-aminopropyl) -terminated polydimethylsiloxane (MW. about.3000) were added to 100mL of toluene. After cooling the solution to 0 ℃ 0.324g (2mmol) of CDI (N, N' -carbonyldiimidazole) were slowly added. After stirring at 0 ℃ for 2h, the solution was heated to 60 ℃ and stirring was continued for 18 h. The organic solution was washed by adding 100mL of deionized water to the mixture. The organic phase was collected over MgSO₄After drying, vacuum distillation was carried out to remove the organic phase to obtain a product (polymer C (Polymer C)). The yield is 80-100%.

In some embodiments, the polymer of the ECD electrolyte may be synthesized as follows:

in the above reaction, 6g (1mmol) of polyethylene glycol (MW-6000), 0.8g (1mmol) of diglycidyl ether-terminated polydimethylsiloxane and 0.1g (1mmol) of Triethylamine (Triethylamine) were added to 100mL of toluene, and the solution was heated to 110 ℃ and reacted for 24 hours. The organic solution was washed by adding 100mL of deionized water to the mixture. The organic phase was collected over MgSO₄After drying, vacuum distillation was carried out to remove the organic phase to obtain a product (polymer D (Polymer D)). The yield is 80-100%

In some embodiments, the solid electrolyte layer 108 comprises an ion conducting polymer and a plasticized polymer with plasticizing groups attached to its side chains, which are chemically linked.

Exemplary polymer electrolytes can include, but are not limited to:

wherein x, y and z are each an integer greater than 0, and

the linkage between the various portions of the backbone, the linkage between the backbone SP and PR, and the linkage between the backbone and CL may be any one or more organic bonds. SP is a soft polymer with a low glass transition temperature (< -20 ℃).

Exemplary PR groups may include, but are not limited to:

exemplary CL groups can include, but are not limited to:

in some embodiments, silicone polymers with plasticizing groups, PEO, and crosslinking groups can be used to synthesize polymers suitable for use in ECD electrolytes. Exemplary reactions may include, but are not limited to:

in the above reaction, a solution comprising ethanol monomer and siloxane is added at-10 ℃ to 10 ℃ in a suitable organic solvent, and triphosgene and base or CDI (N, N' -carbonyldiimidazole) are added, the mixture is stirred at 10 ℃ to 130 ℃ for 1 to 48h, and water is added to the mixture. The organic phase was distilled to remove the solvent to obtain a polymer. The yield is 60-95%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, the solid electrolyte layer 108 may include a brush polymer having a flexible polymer backbone, ionically conductive side chains, and at least one immiscible side chain. Unlike linear polymers, brush polymers have difficulty forming dense packing due to their bulky side chains. Therefore, the introduction of a newly designed brush polymer can be used to avoid the zone crystallization and form an amorphous structure to obtain a completely transparent solid electrolyte.

In some embodiments, to ensure the amorphous structure of the brush polymer, the polymer backbone is comprised of relatively soft, freely rotatable polymer chains. Exemplary flexible polymer chains include one or a combination of at least two of siloxane chains, ethylene chains, acrylate chains, methacrylate chains. In some embodiments, one or more immiscible groups may be introduced into the polymer side chains in addition to the ion conducting groups to disrupt the alignment of the polymer chains. The immiscible group can be, for example, an alkyl chain, an aryl chain, or any group that is immiscible with the ion-conducting group. If the brush polymer is liquid or has a lower mechanical modulus, crosslinking groups may be added to ensure that a solid state morphology is obtained or to increase its mechanical modulus.

Exemplary brush polymers having different side chains for disrupting the alignment of the polymer chains include, but are not limited to:

where x, y and z are each integers greater than 0, and the backbone includes, but is not limited to:

NM is an immiscible group having an alkyl chain, an aromatic group, a combination of alkyl and aromatic groups, or any group that is immiscible with the ion conducting group.

IC is an ion-conducting group, which includes but is not limited to:

CL is a crosslinking group and includes any functional chemical capable of linking two or more monomers. Exemplary CL groups include, but are not limited to:

in some embodiments, the linkage between the various parts of the backbone, the linkage between the backbone and the IC, the linkage between the backbone and the NM, and the linkage between the backbone and the CL may be any one or several organic bonds.

The polymer of the ECD electrolyte can be synthesized using the following two methods. The first method involves forming a backbone polymer and then grafting various side chains onto the backbone to obtain the desired polymer. The second method involves forming monomers or oligomers with different types of side chains and then polymerizing to obtain the desired polymer.

In an example of the first method, siloxane is used as a main chain. For example, the desired polymer may be obtained by reactions including, but not limited to:

in the above reaction, in a suitable organic solvent, a polymethylsiloxane solution, a vinyl-substituted immiscible group, a vinyl-substituted ion-conducting group, a vinyl-substituted crosslinking group, and bubbling with nitrogen gas for about 15 minutes, and then Pt was added as a catalyst. The reaction is protected by nitrogen, the temperature is heated to 40 ℃ to 110 ℃, and after the reaction is carried out for 1 to 24 hours, the mixture after the reaction is sticky. The solvent in the mixture was removed by rotary evaporation to obtain the product. The yield of the process is 60-97%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

Another exemplary polymer for use in the synthesis of ECD electrolytes may be carried out according to the following reaction:

in this reaction, 2.3g (. about.1 mmol) of polymethylsiloxane (molecular weight of 2100-2400), 0.56g (5mmol) of 1-octene, 7.14g (35mmol) of allyloxy (triethoxy-ethylene) methyl ether were added to 100ml of toluene. Sparge with nitrogen for about 15 minutes, then add Karstedt's catalyst 0.4g (0.4mmol) under nitrogen. The reaction was carried out under nitrogen protection and the reaction mixture appeared to be viscous after heating at 50 ℃ for 24 hours. The solvent was removed from the mixture by a rotary evaporator to obtain a product (polymer a). The yield of the process is 80-100%.

Another example polymer of an ECD electrolyte may be formed by the following reaction:

in this reaction, 2.3g (. about.1 mmol) of polymethylhydrosiloxane (molecular weight of 2100-2400), 0.56g (5mmol) of 1-octene, 6.73g (33mmol) of allyloxy (triethoxy) methyl ether, 0.22g (2mmol) of 1, 7-octadiene were added to 100ml of toluene. Sparge with nitrogen for about 15 minutes and add Karstedt's catalyst 0.4g (0.4mmol) under nitrogen. The reaction was carried out under nitrogen protection and the reaction mixture appeared to be viscous after heating at 50 ℃ for 24 hours. The solvent in the mixture was removed by a rotary evaporator to obtain a product (polymer B). The yield of the process is 80-100%.

Another example polymer of an ECD electrolyte may be formed by the following reaction:

in this reaction, 2.3g (. about.1 mmol) of polymethylhydrosiloxane having a molecular weight of 2100,2400, 0.52g (5mmol) of styrene, 6.73g (33mmol) of allyloxy (triethoxy) methyl ether, 0.22g (2mmol) of 1, 7-octadiene were added to 100ml of toluene. Sparge with nitrogen for about 15 minutes and then add Karstedt's catalyst 0.4g (0.4mmol) under nitrogen. The reaction was carried out under nitrogen protection and the reaction mixture appeared to be viscous after heating at 50 ℃ for 24 hours. The solvent in the mixture was removed by a rotary evaporator to obtain a product (polymer C). The yield of the process is 80-100%.

In another example of the first method, 1, 2-polybutadiene is used for the main chain. For example, the desired polymer may be obtained by reactions including, but not limited to:

condition 1: and (4) heating for polymerization. 1, 2-polybutadiene, with or without a free radical initiator, a thiol-substituted immiscible group, a thiol-substituted ion-conducting group, and a thiol-substituted crosslinking group, is mixed in a suitable organic solvent or non-solvent system. The mixture is heated to 40-110 ℃ and reacted for 10 minutes to 24 hours to give a viscous solution or solid. The viscous solution or solid may be used as a target polymer electrolyte, which is coated on a working electrode or a counter electrode to form a solid electrolyte membrane.

In some embodiments, all of the starting materials that are not polymerized (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation of the in situ polymerization under heated conditions.

Condition 2: UV photopolymerization. 1, 2-polybutadiene, including or not including a free radical initiator, a thiol-substituted immiscible group, a thiol-substituted ion-conducting group, and a thiol-substituted crosslinking group, is mixed in a suitable organic solvent or non-solvent system. The mixture is irradiated under UV light for 2-150 minutes to give a viscous solution or solid. The viscous solution or solid may be used as a target polymer electrolyte, which is coated on a working electrode or a counter electrode to form a solid electrolyte membrane.

In some embodiments, all of the starting materials that are not polymerized (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used directly in the device preparation for in situ polymerization under conditions of UV light irradiation.

Exemplary free radical initiators include, but are not limited to: tert-amyl peroxybenzoate, 4, 4-azobis (4-cyanovaleric acid), 1,1 '-azobis (cyclohexanecarbonitrile), 2,2' -azobisisobutyronitrile, benzoyl peroxide 2,2, 2-bis (tert-butylperoxy) butane, 1, 1-bis (tert-butylperoxy) cyclohexane, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl-3-hexyne, bis (1- (tert-butylperoxy) -1-methylethyl) benzene, 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2, 4-pentanedione peroxide, peracetic acid, and potassium persulfate.

In one example of the second method, monomers having different types of side chains are formed and then polymerized to obtain the desired polymer. For example, the desired polymer may be prepared by the following reaction:

condition 1: and (4) heating for polymerization. Monomers having immiscible groups, monomers having ion-conducting groups, and monomers having crosslinking groups, with or without free radical initiators, are mixed in a suitable organic solvent or non-solvent system. The mixture is heated at 40-110 ℃ for 10 minutes to 24 hours to give a viscous solution or solid. The viscous solution or solid may be used as a target polymer electrolyte, which is coated on a working electrode or a counter electrode to form a solid electrolyte membrane.

In some embodiments, all of the starting materials that are not polymerized (referred to as electrolyte precursors or mixtures of electrolyte precursor solutions) can also be used in the device preparation of the in situ polymerization under heating.

Condition 2: UV photopolymerization. Monomers having immiscible groups, monomers having ion-conducting groups, and monomers having crosslinking groups, with or without free radical initiators, are mixed in a suitable organic solvent or non-solvent system. The mixture is irradiated under UV light for 2-150 minutes to give a viscous solution or solid. The viscous solution or solid may be used as a target polymer electrolyte, which is coated on a working electrode or a counter electrode to form a solid electrolyte membrane.

In some embodiments, all of the starting materials that are not polymerized (referred to as electrolyte precursors or mixtures of electrolyte precursor solutions) can also be used for device preparation for in situ polymerization under UV light irradiation conditions.

Exemplary free radical initiators include, but are not limited to: tert-amyl peroxybenzoate, 4, 4-azobis (4-cyanovaleric acid), 1,1 '-azobis (cyclohexanecarbonitrile), 2,2' -azobisisobutyronitrile, benzoyl peroxide 2, 2-bis (tert-butylperoxy) butane, 1, 1-bis (tert-butylperoxy) cyclohexane, 2, 5-bis (tert-butylperoxy) -2, 5-dimethylhexane, 2, 5-bis (tert-butylperoxy) -2, 5-dimethyl-3-hexyne, bis (1- (tert-butylperoxy) -1-methyl-ethyl) benzene, 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl acetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2, 4-pentanedione peroxide, peracetic acid, and potassium persulfate.

In some embodiments, the desired polymer may be prepared by the following reaction:

in this reaction, a norbornene monomer having an immiscible group, a norbornene monomer having an ion conductive group, and a norbornene monomer solution having a crosslinking group are bubbled with nitrogen gas for 15 minutes in a suitable organic solvent. Grubbs' catalyst was then added. The reaction is carried out under the protection of nitrogen, the temperature is heated to 40-110 ℃, the reaction lasts for 10 minutes to 24 hours, and the mixture is sticky after the reaction. The solvent in the mixture was removed by a rotary evaporator to obtain the product. The yield of the process is 60-97%.

In some embodiments, all of the initial starting materials that are not heated (referred to as electrolyte precursors or electrolyte precursor solutions) can also be used in the device preparation for in situ polymerization under heating conditions.

In some embodiments, any one or more of the above-described polymer electrolytes or electrolyte precursors (e.g., all monomers or oligomers that are not polymerized, with or without one or more free radical initiators, with or without a mixture of catalysts) can be mixed with one or more organic or inorganic salts prior to the step of preparing the solid electrolyte thin film of the electrochromic device. Exemplary inorganic salts include, but are not limited toRestricted to Li⁺,Na⁺,K⁺,Mg²⁺,Ca²⁺,Al³⁺And the like, either now known or later discovered. Exemplary organic salts include, but are not limited to, salts that are currently known or later discovered by EMITFSI, EMIOTF, and the like.

In some embodiments, any one or more of the polymer electrolytes disclosed herein can be dissolved in one or more suitable solvents prior to mixing with any one or more of the exemplary salts. The solvent mixes the polymer and salt well and can be removed by evaporation after coating into a film. The polymer electrolyte solution can be applied as a film using any of a variety of conventional coating strategies including, but not limited to, spray coating, spin, slot-and-nip extrusion coating, slot coating, roll-to-roll coating, transfer coating, and wire-bar coating.

Refer to fig. 2. Fig. 2 is a flow chart of a method 200 of making an electrochromic device according to one embodiment of the invention. In step 202, a first transparent electrode is overlaid on a first flexible substrate. The first transparent electrode may include, but is not limited to, ITO (indium-tin oxide), AZO (aluminum zinc oxide), FTO (fluorine doped tin oxide), silver nanowires, graphene, carbon nanotubes, metal mesh, or silver nanoparticles. The first transparent electrode may be coated/deposited using a physical or chemical vapor deposition method (e.g., sputtering). In step 204, an electrochromic layer is coated on a first transparent electrode surface of a first flexible substrate. In step 206, a second transparent electrode is overlaid on a second flexible substrate. The second transparent electrode may include, but is not limited to, ITO (indium-tin oxide), AZO (aluminum zinc oxide), FTO (fluorine doped tin oxide), silver nanowires, graphene, carbon nanotubes, metal mesh, or silver nanoparticles. The second transparent electrode may be coated/deposited using a physical or chemical vapor deposition method (e.g., sputtering). In step 208, the ion storage layer is coated on a second transparent electrode surface of a second flexible substrate.

In step 210, a polymer electrolyte solution or an electrolyte precursor solution is disposed at a surface of the electrochromic layer, or at a surface of the ion storage layer, or at a surface of the electrochromic layer and a surface of the ion storage layer, or at a gap between the electrochromic layer and the surface of the ion storage layer. In step 212, a first flexible substrate and a second flexible substrate are laminated with a partial area of one of the substrates not covered by the other substrate, with an electrolyte interposed between the electrochromic layer and the ion storage layer.

For example, the first flexible substrate (WE) and/or the second flexible substrate (CE) prepared by the above-described method is placed on a flat surface, such as a slate, glass, or the like. A polymer electrolyte solution or an electrolyte monomer/oligomer solution (solid electrolyte precursor) is applied to the first flexible substrate and/or the second flexible substrate by methods including, but not limited to, spray coating, spin coating, slot-and-nip extrusion coating, slot coating, roll-to-roll coating, dimple coating, screen printing, transfer coating, wire-bar coating, and the like. After the electrolyte solution is uniformly coated on one or both of the substrates, the two substrates are combined, and suitable combining methods include, but are not limited to, staggered coverage, and full coverage. Fig. 3A and 3B show schematic views of two lamination arrangements in which a local area of one substrate is not covered by another substrate.

In some embodiments, after the polymer electrolyte solution is uniformly coated on one or both of the substrates, the polymer electrolyte solution is partially dried in an oven (vacuum oven or non-vacuum oven) at room temperature or 60-140 ℃, and then the two substrates are composited, suitable compositing methods include, but are not limited to, staggered coverage, and full coverage.

After compounding, a roller press, a flat plate press, a vacuum press, or other equipment may be used to remove air bubbles from the electrolyte precursor. More specifically, for example, a multilayer thin film device composed of WE, CE and electrolyte precursors can be laminated on a flat-bed laminator for a period of time, e.g., 1-30min, at room temperature under 1 atmosphere, or at elevated temperature (. gtoreq.90 ℃) in the range of 30-500 MP. And stopping the pressing step after the electrolyte layer is defoamed. Alternatively, the multilayer thin-film device is rolled at a speed of 0.5 to 30m/s by a roll press at room temperature or under heating (. gtoreq.90 ℃) to remove air bubbles in the electrolyte layer.

In some embodiments, the polymer electrolyte solution or electrolyte precursor can be uniformly dropped between the CE and the WE by a syringe. WE and CE were rolled together by a roller press with the electrolyte precursor sandwiched therebetween. In some embodiments, the pressure of the roller press is in the range of 1-200MP and the rolling speed is in the range of 0.1-30 m/s. The dropping speed of the electrolyte precursor can be estimated as X Y Z mL/s, where X (cm) is the electrolyte thickness, Y (cm/s) is the roll press speed, and Z is the width of the overlap of WE and CE. The method is suitable for low-cost and large-scale online production of the ECD.

In step 214, the electrolyte solution is cured to produce a finished electrochromic device. In some embodiments, the electrolyte solution may be thermally cured. For example, the electrolyte solution may be cured at 80-120 deg.C at 30-500MP for 1-30 min. For example, the multilayer thin film device can be placed in an oven and baked at a constant temperature of 90 ℃ for 1-30min with complete crosslinking of the solid electrolyte to bond the WE and CE layers to each other to form a solid electrochromic thin film device.

In some embodiments, the laminated device with the polymer electrolyte solution sandwiched between the two electrodes is placed in a vacuum or non-vacuum oven at a temperature in the range of 60-140 ℃ for drying to solidify to form a solid electrolyte, and the WE and CE layers are bonded to each other to form a solid electrochromic thin film device.

In some embodiments, the electrolyte solution may be cured using UV light. In some embodiments, the electrolyte solution is cured to provide an electrolyte layer having a neutral small organic molecule content of less than or equal to 3000 molecular weight less than 20 wt%. In some embodiments, the electrolyte solution is cured to provide an electrolyte layer having a neutral small organic molecule content of less than about 3 wt% and a molecular weight of less than about 3000. When the content of the neutral organic small molecule in the electrolyte layer is too high, the ionic conductivity between the ion storage layer and the electrochromic layer is suppressed. In some embodiments, the electrolyte solution is cured to provide an electrolyte layer that does not contain small neutral organic molecules that can be detected or measured by instrumentation.

In some embodiments, the multilayer thin film device is placed in an oven and baked at a constant temperature of 90 ℃ for 1-30min with complete cross-linking of the solid electrolyte to bond the WE and CE layers to each other to form a solid electrochromic thin film device.

In some embodiments, the method 200 of making further includes a step 216 of removing material from the portions of the first transparent electrode or the second transparent electrode that are not covered by each other. This step serves to remove material over portions of the transparent electrode and expose the surface of the transparent electrode. Methods of removing the electrochromic layer, the ion storage layer and the electrolyte layer from the substrate surface include, but are not limited to, wiping, laser etching and plasma etching. When wiping with a dust-free paper, cloth or the like, a suitable solvent may be used to dissolve the substances on these surface layers. Exemplary wiping solvents include, but are not limited to, acetone, ethanol, and o-xylene, among others. Before wiping, a silicone or other material mold, shaped like the edge to be wiped, can be used as a protector to avoid film peeling and contamination of other areas. When laser etching is used, the device parameters can be adjusted according to the WE, CE and thickness and material properties of the electrolyte layer. For example, laser etching may be performed at a speed of 10-600mm/s, an energy of 10-200w, and a frequency of 10-20000 Hz.

In step 218, wiring of the electrochromic device is performed. For example, the circuit for controlling the electrochromic device is connected to the transparent electrode exposed to the outside. The circuit may be placed by, for example, placing a double-sided conductive tape or conductive paste/ink in the area to form a width of conductive traces in the exposed conductive areas. The conductive leads may be extended by flexible circuit boards, silver paste or copper wires, etc. to connect with a power source.

The all-solid-state electrochromic thin film device prepared by the process can be packaged into various products and used for different application scenes, such as automobiles, airplanes, buildings, sunglasses, medical treatment, education and the like.

Example 1:

1. preparation of electrochromic layer film (WE)

800mg of poly (ethylhexane propylene dioxythiophene) is dissolved in 10mL of o-xylene, magnetic stirring is carried out for 10 hours, and then the obtained solution is uniformly coated on the surface of a nano-silver transparent conductive film (a substrate coated with a nano-silver conductive layer) by a slit coating mode to form an electrochromic layer. And baking the electrochromic layer at the high temperature of 120 ℃ for 30 minutes to obtain an electrochromic layer film, wherein the electrochromic material is well adhered to the flexible conductive substrate. Thereafter, the manufactured electrochromic layer film is cut into a shape 402 as shown in fig. 4 by a die cutter.

2. Preparation of ion storage layer film (CE)

Depositing tungsten trioxide with the thickness of dozens of micrometers on the surface of the nano-silver transparent flexible conductive film in a magnetron sputtering mode at room temperature to prepare the ion storage layer film. Thereafter, the ion storage layer film is cut into a shape 404 as shown in fig. 4 by a die cutter, the shape 404 being the same as the shape 402.

3. Preparing an electrolyte layer

The electrolyte layer was prepared using a brush polymer. Mixing a polymer, a lithium salt and an ultraviolet curing initiator according to a mass ratio of 45:15:10, magnetically stirring for 30 minutes, and ultrasonically treating for 30 minutes to defoam the mixture to prepare a precursor solution. As shown in fig. 5, a precursor 502 is added to the edge of the electrochromic layer 504, and the precursor is uniformly coated on the surface of the electrochromic layer 506 by a bar coater 508.

4. Laminating and curing

As shown in fig. 6, the ion storage layer is offset-superimposed on the electrolyte-coated electrochromic layer, and the ion storage layer is disposed opposite to the electrochromic layer. The laminated film is then rolled by a roll press to remove air bubbles between the film layers. And after bubble removal, placing the laminated film under UV light, completely crosslinking the electrolyte precursor to form a solid electrolyte, and well bonding the electrochromic layer and the ion storage layer together to prepare the ECD device.

5. Exposing conductive regions and wiring

The electrolyte and the electrochromic layer attached to the reserved wiring region (stripe region) were wiped off with acetone, and the ion storage layer was etched with laser to expose the conductive layer. Copper wires 702 are adhered to the exposed conductive layer area and are extended to be led out as positive and negative electrodes, wherein the lead connected with the electrochromic layer is the positive electrode, and the lead connected with the ion storage layer is the negative electrode. The layout and wiring of the leads are shown in fig. 7.

Example 2

1. Preparation of electrochromic layer film (WE)

800mg of electrochromic polymer (copolymer of 2, 5-dibromo-and 2, 5-tributylstannyl-2-ethyl-hexyloxy-substituted ethylhexane-3, 4-propylenedioxythiophene) (ProDOT- (CH)₂OEtHx)₂And 4, 7-dibromo-2, 1, 3-Benzothiadiazole (BTD)) in 10mL of o-xylene, magnetically stirring for 10 hours, and then uniformly coating the obtained solution on an ITO transparent conductive film by a spin coating manner to form an electrochromic layer. And baking the electrochromic layer at the high temperature of 120 ℃ for 30 minutes to obtain an electrochromic layer film, wherein the electrochromic material is well adhered to the flexible conductive substrate. And then, cutting the prepared electrochromic layer film into a preset shape by a die cutting machine.

2. Preparation of ion storage layer film (CE)

At room temperature, TiO will be doped or undoped₂Nb of₂O₅And the printing ink is coated on the surface of the ITO transparent flexible conductive film in a slit extrusion type coating mode, and the thickness of the printing ink is about tens of nanometers, so that the ion storage layer film is prepared.

3. Preparing an electrolyte layer

The electrolyte layer was prepared using a brush polymer. Mixing a polymer, a lithium salt and a thermosetting initiator according to a mass ratio of 50:45:5, magnetically stirring for 10 minutes, and performing ultrasonic treatment for 10 minutes to defoam the mixture to prepare a precursor solution. And uniformly coating the precursor on the surface of the electrochromic layer by a screen printing mode.

4. Laminating and curing

And the ion storage layer is superposed on the electrochromic layer coated with the electrolyte in a staggered manner, and the ion storage layer and the electrochromic layer are arranged oppositely. The laminated films are then laminated by a vacuum laminator to remove air bubbles between the film layers by high pressure. And after the bubbles are removed, the laminated film is placed at the temperature of 100 ℃ for curing for 10 minutes, the electrolyte precursor is completely crosslinked to form a solid composite material, and the electrochromic layer and the ion storage layer are well bonded together to prepare the ECD device.

5. Exposing conductive regions and wiring

The electrolyte and WE attached to the reserved wiring region (stripe region) were wiped off with acetone, and the ion storage layer was etched with laser to expose the conductive layer. And arranging a silver wire or a silver adhesive tape in the exposed conducting layer area, and fixing the FPC through the silver adhesive to extend and lead out to be used as a positive electrode and a negative electrode, wherein the lead connected with the electrochromic layer is the positive electrode, and the lead connected with the ion storage layer is the negative electrode.

Example 3:

1. preparation of electrochromic layer film (WE)

WE was cut into 2cm × 2cm squares by a die cutter, and the rest of the procedure was the same as in example 1.

2. Preparation of ion storage layer film (CE)

CE was cut into a square of 2 cm. times.2 cm by a die cutter, and the rest of the procedure was the same as in example 2.

3. Preparing an electrolyte layer

Same as in example 1.

4. Laminating and curing

The ion storage layer is superimposed in a staggered manner on the electrolyte-coated electrochromic layer. The laminated films are then laminated by a vacuum laminator to remove air bubbles between the film layers by high pressure. After bubble removal, the laminated film is placed under UV light, the electrolyte precursor is completely crosslinked to form a solid composite material, and WE and CE are well bonded together to prepare the ECD device.

5. Exposing conductive regions and wiring

The electrolyte and WE attached to the reserved wiring region (stripe region) were wiped off with acetone, and the ion storage layer was etched with laser to expose the conductive layer. And adhering copper wires on the exposed conductive layer area, and extending and leading out the copper wires to be used as positive and negative electrodes, wherein the lead connected with WE is the positive electrode, and the lead connected with CE is the negative electrode.

Example 4

1. Preparation of electrochromic layer film (WE)

1000mg of poly (ethylhexane propylene dioxythiophene) is dissolved in 10mL of o-xylene, magnetic stirring is carried out for 10 hours, and then the obtained solution is coated on the nano-silver transparent conductive film in a slit coating mode to form a WE coating. And baking the WE coating at a high temperature of 120 ℃ for 30min to obtain a WE film, wherein the electrochromic material is well adhered to the flexible conductive substrate. The resulting WE film was then cut by a die cutter into the shape 802 shown in fig. 8A.

2. Preparation of ion storage layer film (CE)

Prussian blue with a functionalized ligand is dispersed and suspended in alcohol, and is coated on the surface of the transparent FTO flexible conductive substrate by means of slit coating. Then, it was baked at 100 ℃ for 20min to obtain a CE film. The resulting CE film was cut by a die cutter into shape 804 as shown in fig. 8A, and shape 804 was the same as shape 802.

3. Preparing an electrolyte layer

Same as in example 1.

4. Laminating and curing

As shown in fig. 8B, the ion storage layer is offset superimposed on the electrolyte-coated electrochromic layer. The laminated film is then rolled by a roll press to remove air bubbles between the film layers. After the bubble removal, the laminated film is UV light-cured to manufacture the ECD device.

5. Exposing conductive regions and wiring

The electrolyte attached to the reserved wiring region (stripe region), WE802, and CE804 were wiped off with acetone. A silver wire or tape is provided over the exposed conductive layer area to prepare circuit 806. And directly extending and leading out the conductive adhesive tape to be used as a positive electrode and a negative electrode, wherein the leading-out part of the electrochromic layer is the positive electrode, and the leading-out part of the ion storage layer is the negative electrode. The layout and wiring of the leads are shown in fig. 8C.

Example 5

1. Preparation of electrochromic layer film (WE)

WE was cut into a rectangle of 4cm × 20cm by a die cutter, and the rest of the procedure was the same as in example 1.

2. Preparation of ion storage layer film (CE)

The CE was cut into a rectangle of 4cm by 20cm by a die cutter, and the rest of the procedure was the same as in example 2.

3. Preparing an electrolyte layer

Same as in example 1.

4. Laminating and curing

A rectangular all-solid-state electrochromic device of 4cm × 20cm was prepared by cutting with a die cutter, and the remaining steps were the same as in example 1.

Example 6

1. Preparation of electrochromic layer film (WE)

600g of an electrochromic polymer (copolymer of 2, 5-dibromo-and 2, 5-tributylstannyl-2-ethyl-hexyloxy-substituted ethylhexane-3, 4-propylenedioxythiophene) (ProDOT- (CH)₂OEtHx)₂And 4, 7-dibromo-2, 1, 3-Benzothiadiazole (BTD)) are dissolved in 10L o-xylene, the mixture is magnetically stirred for 10 hours, and then the obtained solution is uniformly coated on a coiled PET-ITO transparent conductive film in a roll-to-roll coating mode to form an electrochromic coating. The width of the PET substrate was 50 cm. Then, the film of the applied electrochromic layer was baked at a high temperature of 140 ℃ for 3 minutes to obtain a WE film, and the WE film was wound.

2. Preparation of ion storage layer film (CE)

Prussian blue with a functionalized ligand is dispersed and suspended in alcohol, and is coated on a coiled PET-ITO transparent conductive film in a roll-to-roll coating mode. The width of the PET substrate was 50 cm. Then, the coated film was baked at a high temperature of 120 ℃ for 2 minutes to obtain a CE film, and the CE film was wound.

3. Preparing an electrolyte layer

Same as in example 1.

4. Laminating and curing

Referring to fig. 9, CE film 902 and WE film 904 are pressed together in a roll press 906 with the ion storage layer disposed opposite the electrochromic layer. The speed of the roller press 906 was 5 m/s. The dropping speed of the electrolyte precursor 908 was 25 mL/s. Meanwhile, as shown in fig. 9, the injector 909 uniformly drops the electrolyte precursor between the CE thin film 902 and the WE thin film 904. The laminated films were exposed to UV light, the electrolyte crosslinked to form a solid composite, and WE904 and CE902 were well bonded together to prepare an ECD device.

5. Exposing conductive regions and wiring

And cutting the large-size all-solid-state device into a required shape by adopting laser half-cutting. The electrolyte, CE and WE attached to the reserved wiring regions (stripe regions) were then wiped off with acetone. And adhering copper wires on the exposed conductive layer area, and extending and leading out the copper wires to be used as positive and negative electrodes, wherein the lead connected with WE is the positive electrode, and the lead connected with CE is the negative electrode.

Example 7

1. Preparation of electrochromic layer film (WE)

600mg of an electrochromic polymer (copolymer of 2, 5-dibromo-and 2, 5-tributylstannyl-2-ethyl-hexyloxy-substituted ethylhexane-3, 4-propylenedioxythiophene) (ProDOT- (CH)₂OEtHx)₂And 4, 7-dibromo-2, 1, 3-Benzothiadiazole (BTD)) in 10mL of o-xylene, magnetically stirring for 10 hours, and then uniformly coating the obtained solution on a flexible ITO transparent conductive film of 10cm × 10cm by a slit coating method to form a WE coating. The coated WE coating was baked at high temperature 80 ℃ for 30 minutes to obtain WE film with electrochromic material adhering well to the flexible conductive substrate.

2. Preparation of ion storage layer film (CE)

400mg of poly (nitrosylnitrosylstyrene) is dissolved in 10ml of N-methyl-2-pyrrolidone and magnetically stirred for 10 hours, and then the resulting solution is coated on a flexible ITO transparent conductive film of 10cm × 10cm by a slit coating method to form a CE coating. The coated CE coating was baked at 100 ℃ for 30 minutes to obtain a CE film.

3. Preparing an electrolyte layer

The solid electrolyte polymer of the present embodiment is a plasticized linear polymer and an ion-conductive polymer, which are chemically bonded. The polymer and the lithium salt were mixed at a mass ratio of 60: 40. After magnetic stirring for 30 minutes, the mixture was defoamed using ultrasonic vibration for 30 minutes to obtain a precursor solution ready for use. The precursor was dropped uniformly between the CE film and the WE film by a syringe. And the WE and the CE were pressed by a roll press, and the electrolyte precursor was between the WE and the CE. The pressure of the roller press was 100MP and the rolling speed was 10 m/s. The speed of precursor instillation is 10 mL/s. The laminated film was then cured at high temperature 100 ℃ for 10 minutes to form a solid composite, and the WE and CE were well bonded together.

4. Exposing conductive regions and wiring

The electrolyte and WE attached to the reserved wiring region (stripe region) were wiped off with acetone, and the ion storage layer was etched with laser to expose the conductive layer. Copper wires 702 are adhered to the exposed conductive layer area, and the FPC is fixed by silver paste to lead out the positive and negative electrodes, wherein the lead connected to WE is the positive electrode and the lead connected to CE is the negative electrode.

For liquid or gel state electrolytes, the lack of physical support requires special design and precise sealing of the chamber containing the electrolyte, which results in liquid or gel state electrolytes that are less robust and less prone to bending. Embodiments of the present invention disclose a solid electrolyte layer for an all-solid electrolyte. The disclosed ECDs can be curved or shaped at any angle between 0-360 degrees and can have a small radius of curvature (e.g., as low as 2.5cm), indicating that the ECDs of the present invention can be adapted for use with surfaces of any shape and any curvature. For example, FIG. 10 shows the simultaneous change in light transmittance when the thin film all solid ECDs are bent at different angles and the test voltage is switched from-1.2V to 1.5V. In this example, the ECD was bent to 45 degrees with a radius of curvature of 7.8 cm. One of the most extreme examples in this embodiment is the radius of curvature of 4.2cm obtained by bending the ECDs to 90 degrees, which indicates that the all-solid ECDs of the present invention have the potential to be used in most scenes, such as skylights, rearview mirrors, architectural glass, and the like. In contrast, the related art liquid or gel ECD requires a great deal of effort in sealing and packaging if it is to achieve significant flexure without causing problems (e.g., WE or CE damage, WE and CE contact with each other, etc.). The ECDs of the present disclosure utilize an all-solid electrolyte layer without such excessive requirements for sealing and packaging.

Fig. 11 is a picture of an ECD during operation in an exemplary embodiment. Shown in fig. 11(a) is the ECD in an unbent, colored/darkened state (top) and a lightened state (bottom). As shown in fig. 11(b), the ECD is bent in a nearly semicircular shape in a colored/darkened state. As shown in fig. 11(c), the ECD is curved in an approximately semicircular shape in a lighted state. As shown in fig. 11(d), the ECD is curved in a circular shape and in a lighted state. The ECD is shown in fig. 11(e) in a colored/darkened state bent into a circular shape. Therefore, the ECD device prepared by the embodiment of the application has flexible and stable characteristics.

The all-solid-state ECDs of the present invention can be rapidly switched between coloring and brightening, for example, the switching time can be as fast as 0.1s-1 s. For a 2cm × 2cm ECD, the ECD was switched between potentials of-1.2V and 1.5V at intervals of 1s, and the change in light transmittance was measured. Results as shown in fig. 12, the optical contrast for the ECD with 1s switching can reach about 90% at full switching, indicating that the tested solid state ECD has fast switching kinetics.

Since the electrolyte layer of the present invention is in a solid state, an electrolyte membrane as thin as, for example, 0.1 μm can be manufactured. Electrolyte layers down to, for example, 5 μm in thickness can be readily prepared by processes known in the art that are easy and inexpensive to manufacture, including, for example, roll pressing, plate pressing or vacuum pressing, and thus very thin all-solid ECDs, for example, 25 μm, can be further prepared. Each layer thickness and overall thickness of the ECD can be further reduced. The all-solid-state ECD disclosed by the invention has a very thin thickness, thereby being beneficial to being applied to a small-sized integrated system.

Roll, plate, or vacuum pressing processes cannot be used for ECDs of liquid or gel electrolytes because the viscosity of the liquid or gel electrolyte is very low. However, the all-solid ECD of the present invention can be applied to continuous manufacturing and low-cost processes such as roll-to-roll coating and roll-to-roll processes for low-cost mass on-line production, and can be easily packaged into various application products, due to its stable structure and high temperature resistance.

Further, no delamination or many side reactions occur at the WE/electrolyte, CE/electrolyte interfaces due to the use of solid electrolytes. Thus, the ECDs of the present invention have better cycle performance. The solid ECD of the invention requires low driving voltage (as low as 1.5V), and is suitable for application scenes powered by batteries.

The ECDs prepared by the method can be used for automobile anti-glare rearview mirrors. Fig. 13A is an exploded view of an anti-glare rear view mirror 1300 including an ECD in one embodiment. Fig. 13B is a schematic diagram of a cross-sectional view of the anti-glare rear view mirror 1300. The anti-glare rear view mirror 1300 includes a mirror 1310, an adhesive layer 1320, a solid state ECD1330, a glass substrate 1340, and a seal 1350.

The reflector 1310 has two surfaces, and a reflective layer is disposed on a surface facing the adhesive layer 1320, wherein the reflective layer is made of one or a combination of at least two of pure metal (e.g., cadmium, silver, aluminum, rhodium, iridium, etc.), alloy (e.g., copper, silver alloy, etc.), non-metallic material (e.g., silicon dioxide, titanium dioxide with polymer matrix, etc.), and mixed material (e.g., metal and non-metallic material). In some embodiments, the side of the mirror facing the air may also be provided with a reflective layer to act as a mirror. Illustratively, the thickness of the reflector ranges from 0.01 to 0.5mm, the thickness of the reflector ranges from 0.5 to 2.5mm, and the reflectivity of the reflector ranges from 50% to 100%. The mirror may be flat or may have a curvature. The curvature radius of the non-planar mirror ranges from 10 mm to 1500 mm.

The adhesive layer 1320 is a transparent adhesive. Exemplary clear adhesives include OCAs (optically clear adhesives) such as resin OCAs, liquid OCAs, or solid OCAs, hot melt adhesives including, but not limited to, EVA (ethylene vinyl acetate film), PVB (polyvinyl butyral film), and the like. Exemplary curing methods include moisture curing, thermal curing, UV (ultraviolet) curing, and the like. When the optically transparent adhesive is coated on the surface of the electrochromic rear view mirror or encapsulated in the inside thereof, UV curing or moisture curing is generally used. When hot melt adhesives are used, the heat curing is usually carried out during the lamination process. The light transmittance of the adhesive layer can be between 80% and 100%. In addition, the adhesive layer should be selected to have a refractive index close to that of glass, typically between 1.1 and 1.6. The thickness of the adhesive layer may vary from 0.05 mm to 0.5 mm.

An all solid state thin film electrochromic device (ECD)1330 is consistent with the foregoing disclosure, with the ECD1330 having a thickness ranging from 0.02 to 3.0 mm.

The light transmittance of the glass substrate 1340 is between 50% and 100%. Typically, the surfaces not facing the EC mirror need to be modified to eliminate reflectivity, such that the reflectivity is less than 4%. The glass may be flat, curved, or curved with varying curvature. For non-planar glass substrates, the radius of curvature may range from 10 mm to 1500 mm.

The sealing member 1350 has good adhesion to glass and has waterproof property. Exemplary sealants include butyl rubber, epoxy rubber, polyurethane, acrylic, and the like. Such sealants are required to have a curing volume shrinkage (including thermal curing, UV curing, moisture curing, etc.) of 0.5% to 2%, and after curing thereof, the glass substrate 1340 and the reflecting mirror 1310 can be closely adhered together to obtain a better encapsulation effect. The curing method may be selected based on the characteristics of the sealant.

At least two exemplary manufacturing processes are described below, depending on the type of adhesive, for encapsulating the preassembled ECD into a rearview mirror, which includes both flat and curved surfaces.

The method A comprises the following steps: using Optical Clear Adhesive (OCA)

1. Preparing materials: the OCA layers and ECDs are cut to the desired shape and size using a die cutter, laser, or other known techniques. The gauge parameters are adjusted to ensure that the cutting process is performed smoothly. The setting parameters of the die cutting machine and the laser machine are determined according to the thickness and the characteristics of the material. For example, when an OCA having a thickness of 100um is used, the moving speed of the laser machine may be 1mm/s to 600mm/s, the energy may be 1w to 500w, and the frequency range may be 1Hz to 10000 Hz.

1.1 thermoforming of the material: when manufacturing a curved rearview mirror, the electrochromic thin film device may first be hot-bent to form a curved surface having a certain curvature (e.g., the radius of curvature may range from 50mm to infinity). As shown in fig. 14A and 14B, the electrochromic thin film device can be pressed in an oven at 50-100 ℃ for 5-30min to perform hot bending using a curved mold with a preset shape and curvature, wherein whether the oven needs vacuum depends on the hardness of the mold. During the hot bending process, the ECD can be made to maintain the same curvature as the glass substrate/mirror, so this step facilitates the step 2 of bonding. However, this step is optional for use of the OCA to make curved rearview mirrors, since the ECD of the present invention is flexible and easily bends to conform to any shape or curvature of surface. For the preparation of flat rear view mirrors, this step can be omitted.

2. Attaching an adhesive layer on the glass substrate/mirror (half assembly): the process varies depending on the type of adhesive used (liquid or solid). For solid or viscous adhesives, the adhesive layer may be applied to the glass substrate/mirror by roll pressing (see details below at 2.1) or vertical pressing (see details below at 2.2). In contrast, flat rear view mirrors are easier to manufacture. For curved rearview mirrors, customized tooling can be used to aid in the machining, including but not limited to jigs that have the same curvature as on the glass substrate/mirror. For liquid adhesives, the liquid adhesive may be applied to the glass substrate/mirror surface using, for example, a dispenser, a spray gun, a screen printer, a coater, etc., and then the lamination is usually performed using a vertical lamination method.

2.1 rolling method: fig. 15 shows a manufacturing process diagram of the rearview mirror according to one embodiment. The glass substrate/reflector (including surface shapes such as plane, curved surface, spherical surface and the like) is fixed on a special fixture of the rolling platform through a mold, and the hardness of the mold is lower than that of steel, and the mold can be made of rubber, silica gel, polyurethane, polyacrylate, polyester, epoxy resin and the like. For curved products, the mold can be customized to the curvature of the glass substrate/mirror. Typically the shore hardness of the mould is greater than 50. The curvature deviation between the roller and the glass substrate/mirror is less than 10%. And adhering the edge of the transparent adhesive layer to the edge of the glass substrate. The material of the transparent adhesive layer includes, but is not limited to, hot melt adhesive, OCA, etc., and the thickness thereof ranges from 0.5 to 500 μm. The thickness of the glass substrate ranges from 0.5 to 1.8 mm. The adhesive layer and the glass substrate/mirror are rolled by a roller as shown in fig. 16A and 16B. The roller is made of a material having a hardness lower than that of steel, and may be, for example, rubber, silicone, polyurethane, polyacrylate, polyester, epoxy resin, or the like. The rollers may be customized to the curvature of the glass substrate/mirror. Typically the roller has a shore hardness of less than 100. The curvature deviation between the roller and the glass substrate/mirror is less than 10%. The pressure applied to the adhesive layer and the glass substrate/mirror during the rolling process is in the range of 100pa to 1000 kpa.

2.2 vertical pressing method: fig. 17 is a view illustrating a manufacturing process of a rearview mirror according to another embodiment. And fixing the glass substrate/reflector (including surface shapes such as planes, curved surfaces, spherical surfaces and the like) on a corresponding mold with a preset curvature. The deviation of the radii of curvature of the mold and the glass substrate/mirror ranges from 0 to 100 mm. The adhesive layer is fixed on another mold with a preset curvature based on a glass substrate/mirror. The deviation of the radius of curvature of the other mold and the glass substrate/mirror is in the range of 0-500 mm. The mold holding the glass substrate/mirror and the other mold holding the adhesive layer are separated by a distance and held in place by a device to avoid contact between the two prior to pressing. Vacuumizing the equipment, when the vacuum reaches a preset value, generally more than 95%, pressing another mould for fixing the adhesive layer on the mould for fixing the glass substrate/reflector through an engine or a gear of a pressing machine, and pressing for 5s-15min under the pressure range of 1kpa-1000 kpa.

3. ECD was attached to the glass substrate/mirror (other half assembly): ECD was attached to the glass substrate/mirror with the adhesive layer already attached as prepared in step 2. Exemplary methods include, but are not limited to, rolling, vertical pressing, and the like.

3.1 rolling method: fig. 18 shows a manufacturing process diagram of the rearview mirror according to one embodiment. The glass substrate/reflector (including surface shapes such as plane, curved surface, spherical surface and the like) to which the adhesive layer is attached is fixed on a special fixture of the rolling platform through a mold, and the hardness of the mold is lower than that of steel, and the mold can be made of rubber, silica gel, polyurethane, polyacrylate, polyester, epoxy resin and the like. For curved products, the mold can be customized to the curvature of the glass substrate/mirror. Typically the shore hardness of the mould is greater than 50. The curvature deviation between the roller and the glass substrate/mirror is less than 10%. The edge of the ECD is glued to the edge of the glass substrate/mirror to which the adhesive layer has been attached. The ECD and the glass substrate/mirror to which the adhesive layer has been attached are rolled by a roller as shown in fig. 16A and 16B. The roller is made of a material having a hardness lower than that of steel, and may be, for example, rubber, silicone, polyurethane, polyacrylate, polyester, epoxy resin, or the like. The rollers may be customized to the curvature of the glass substrate/mirror. Typically the roller has a shore hardness of less than 100. The curvature deviation between the roller and the glass substrate/mirror is less than 10%. The pressure applied to the adhesive layer and the glass substrate/mirror during the rolling process is in the range of 100pa to 1000 kpa.

3.2 vertical pressing method: fig. 19 is a view showing a manufacturing process of a rearview mirror according to another embodiment. And fixing the glass substrate/reflector (including surface shapes such as planes, curved surfaces and spherical surfaces) to which the adhesive layer is attached on a corresponding mold with a preset curvature. The deviation of the radii of curvature of the mold and the glass substrate/mirror ranges from 0 to 100 mm. The adhesive layer is fixed on another mold with a preset curvature based on a glass substrate/mirror. The deviation of the radius of curvature of the other mold and the glass substrate/mirror is in the range of 0-500 mm. The mold for fixing the glass substrate/mirror to which the adhesive layer has been applied and the other mold for fixing the adhesive layer are separated by a certain distance and fixed with equipment to avoid contact between the two before pressing. Vacuumizing the equipment, when the vacuum reaches a preset value, generally more than 95%, pressing another mould for fixing the adhesive layer on the mould for fixing the glass substrate/reflector to which the adhesive layer is attached through an engine or a gear of a pressing machine, and pressing for 5s-15min under the pressure range of 1kpa-1000 kpa.

4. Combining two half-assemblies: fig. 20 shows a flowchart of manufacturing a rearview mirror according to an embodiment. One half-module is prepared by step 1 and the other half-module is prepared by step 2. In the combining step, the two half assemblies can be combined by various methods including, but not limited to, pressing with or without heat, with or without vacuum. And fixing the glass substrate/reflector (including surface shapes such as planes, curved surfaces and spherical surfaces) to which the adhesive layer is attached on a corresponding mold with a preset curvature. The deviation between the radius of curvature of the mold and the radius of curvature of the glass/mirror may be between 0mm and 100 mm. The glass substrate/mirror (including surface shapes such as flat, curved, spherical, etc.) to which the ECD has been attached is fixed on another mold corresponding to a predetermined curvature. The deviation of the radius of curvature of the other mold and the glass substrate/mirror is in the range of 0-500 mm. The mold for fixing the glass substrate/mirror to which the adhesive layer has been attached and the other mold for fixing the glass substrate/mirror to which the ECD has been attached are separated by a certain distance and fixed by a device to prevent contact between them before press-fitting. Vacuumizing the equipment, when the vacuum reaches a preset value, generally more than 95%, pressing another mould for fixing the adhesive layer on the mould for fixing the glass substrate/reflector to which the adhesive layer is attached through an engine or a gear of a pressing machine, and pressing for 5s-15min under the pressure range of 1kpa-1000 kpa.

5. Edge sealing with a suitable sealant: the edge sealing step can be performed after the completion of the 4 steps (as described in 5.1), or can be combined in the 4 steps according to specific conditions (such as the properties of the sealant). If the sealant has a relatively low viscosity, typically between 100cps and 10,000cps, method 5.1 is used. When the viscosity of the sealant is very high, typically ranging from 100,000cps to 2,000,000cps, method 5.2 is used. When the viscosity is intermediate (neither too high nor too low), both methods can be used.

5.1 as shown in fig. 21, a flow chart of edge sealing of an embodiment is shown. Referring to fig. 21, after the foregoing 4 steps are completed, the sealant is uniformly dropped onto the edge between the reflector 1310 and the glass substrate 1340 by a suitable device (including but not limited to a glue syringe, hot melt glue, etc.). The amount of the sealant is controlled to avoid bubbles and overflow. The sealant flow rate may range from 0.001mL/min to 50mL/min, depending on the thickness and width of the seal, with an exemplary seal having a thickness ranging from 0.1mm to 3mm and an exemplary width ranging from 0.01mm to 5 mm. Exemplary syringe needles range from 0.01mm to 5mm in diameter. After the sealant is dispensed, the sealant is cured by a suitable curing method including, but not limited to, radiation (e.g., UV) curing, thermal curing, moisture curing, and other methods known in the art.

5.2 the edge sealing step is combined in any of the foregoing steps 2 through 4, and the sealant is uniformly dropped onto the edge of the reflector 1310 or the glass substrate 1340 by a suitable device (including but not limited to a glue injector, a hot melt glue injector, etc.). As shown in fig. 22A and 22B, after the step 2, the sealant is dropped, that is, after the adhesive layer is adhered to the surface of the glass substrate/mirror, a circle of sealant is uniformly disposed on the surface of the adhesive layer along the edge of the glass substrate/mirror, and then other steps after the step 2 are performed. Another example embodiment is shown in fig. 23, after the sealing member is provided after step 3, i.e., after the ECD is adhered to the surface of the glass substrate/mirror, a ring of sealant is uniformly provided on the surface of the ECD along the edge of the glass substrate/mirror, and then the other steps after step 3 are performed.

The method B comprises the following steps: using hot-melt adhesives

1. Preparing materials: the layer of hot melt adhesive and the ECD are cut to the desired shape and size using a die cutter, laser, or other known techniques. The gauge parameters are adjusted to ensure that the cutting process is performed smoothly. The thickness of the hot melt adhesive may range from 0.01mm to 5 mm.

2. Material thermoforming: for the preparation of flat rear view mirrors, this step can be omitted. This step is optional for the preparation of curved mirrors, but is advantageous for maintaining the ECD in a pre-set fixed shape to eliminate possible defects caused by subsequent device bending. When the curved rearview mirror is prepared, a curved mold with a preset shape and curvature can be used, and the electrochromic thin film device is pressed in an oven with the temperature of 50-100 ℃ for 5-30min to be subjected to hot bending to form a curved surface with a certain curvature, wherein the curvature radius range can be from 50mm to infinity.

3. Laminating glue layer, rearview mirror and glass substrate: the glue layer, the mirror, and the glass substrate are laminated in this order as shown in fig. 13A and 13B. The adhesive layer is then hot melted and cured, after which the five-layer structure is bonded together as a unit.

4. Sealing edges by using sealant: the specific embodiment of this step is the same as step 5 in method a.

Example 8: using method A to manufacture a curved EC mirror with curvature radius of 1200mm

800. Preparing materials: the material was cut with a laser machine, wherein the thickness of the OCA was 100 μm, the moving speed of the laser machine was 100mm/s, the energy was 10w, the frequency was 100Hz, and the height of the laser from the adhesive layer was 0.2 cm.

810. Material thermoforming: placing the electrochromic thin film device between custom molds (an upper mold and a lower mold) with the curvature radius of 1200mm, pressing the electrochromic thin film device in an oven at 100 ℃ for 15 minutes, and taking out and cooling to room temperature. The electrochromic thin film device was thermally bent to form a curved shape with a radius of curvature of 1200 mm.

820. The adhesive layer was adhered to the glass substrate by a rolling process (half assembly): the glass substrate is fixed on a special clamp of the rolling platform through a mold made of polyurethane, and the curvature radius of the mold is the same as that of the glass substrate and is 1200 mm. The shore hardness of the mold was 85. The edge of the transparent adhesive layer (thickness 150 μm) was aligned with the edge of the glass substrate (thickness 1.1 mm). And rolling the adhesive layer and the glass substrate by a rubber roller, wherein the curvature radius of the rubber roller is the same as that of the glass substrate. The roller had a shore hardness of 65. During the rolling process, the pressure applied to the adhesive layer and the glass substrate was 1 kpa.

830. ECD was attached to the mirror by rolling (the other half of the assembly): the reflector with the adhesive layer is fixed on a special fixture of the rolling platform through a mold made of polyurethane, and the curvature radius of the mold is the same as that of the glass substrate and is 1200 mm. The shore hardness of the mold was 85. The edge of the ECD is aligned with the edge of the transparent adhesive layer, and then the ECD and the adhesive layer on the surface of the reflector are rolled by a squeegee, the radius of curvature of the squeegee is the same as that of the glass substrate. The roller had a shore hardness of 65. During the rolling process, the pressure applied to the adhesive layer and the glass substrate was 10 kpa.

840. Combining two half-assemblies: the glass to which the adhesive layer was attached was fixed on a surface of a mold having a curvature radius of 1250mm, and the mirror to which the ECD was attached was fixed on another surface of the mold having a curvature radius of 1150 mm. The two molds are separated by a distance and are held in place by equipment to avoid contact between the two prior to pressing. Vacuumizing the equipment, pressing the mold fixedly attached with the glass with the adhesive layer on the mold fixedly attached with the reflector with the ECD after the vacuum reaches 99.5%, and pressing for 1min under the pressure of 100 kpa.

850. Edge sealing with UV curing glue: the UV curable sealant was uniformly dropped onto the edge between the mirror and the glass substrate. The flow rate of the sealant was 0.5mL/min, and the diameter of the syringe needle was 0.5 mm. After the addition of the sealant, the sealant was cured by UV light with an energy of 2000mJ/cm 2.

Example 9: a curved EC mirror with a curvature radius of 1200mm is manufactured by the method A

900. Preparing materials: the same as in example 8.

910. The adhesive layer was adhered to the glass substrate by a vertical lamination method (half assembly): the glass substrate was fixed on a mold having a radius of curvature of 1250 mm. The adhesive layer was fixed to another mold having a radius of curvature of 1150 mm. The mold to which the glass substrate is fixed and the mold to which the adhesive layer is fixed are separated by a certain distance and fixed by a device to avoid contact between them before press-fitting. And vacuumizing the equipment, pressing the mould fixedly attached with the adhesive layer on the mould fixedly attached with the glass substrate when the vacuum reaches 99.5%, and pressing for 30s under the pressure of 100 kpa.

920. The ECD was attached to the mirror by vertical pressing (the other half of the assembly): the reflector with the adhesive layer attached thereto was fixed on a mold having a curvature radius of 1250 mm. The ECD was fixed to another mold with a radius of curvature of 1150 mm. The mold to which the reflector with the adhesive layer attached thereto is fixed and the mold to which the ECD is fixed are separated by a certain distance and fixed by a device to prevent contact between them before press-fitting. Vacuumizing the equipment, pressing the mold for fixing the ECD on the mold for fixing the reflector attached with the adhesive layer after the vacuum reaches 99.5%, and pressing for 30s under the pressure of 100 kpa.

930. Combining two half-assemblies: the same as in example 8.

940. Edge sealing with UV curing glue: the same as in example 8.

Example 10: making a planar EC mirror by method B

1000. Preparing materials: the material was cut with a die cutter, wherein the equipment parameters for PVB cutting were as follows, using a custom-made die of the same shape as the glass substrate, cutting was performed at a pressure of 5t, the die height from the PVB being 1.0 cm.

1010. Laminating glue layer, rearview mirror and glass substrate: the adhesive layer, the mirror and the glass substrate were laminated in the order as shown in fig. 24, and they were put into a hot press apparatus having vacuum, heating and pressurizing functions. The five-layer structure was bonded together as a whole after pressing at 140 c under a vacuum of 99% for 30 minutes and a pressure of 6 bar.

1020. Edge sealing with a suitable sealant: the same as in example 8.

Example 11: making a curved EC mirror by method B

1100. Preparing materials: and cutting the material by using a laser machine, wherein the parameters of the PVB cutting equipment are as follows, the moving speed of the laser machine is 100mm/s, the energy is 100w, the frequency is 100Hz, and the height of the laser from the adhesive layer is 0.5 cm.

1110. Material thermoforming: PVB was placed between custom molds with a radius of curvature of 1200mm, pressed in an oven at 100 ℃ for 15min, and then taken out and cooled to room temperature. The PVB was thermally bent to form a curved shape with a radius of curvature of 1200 mm.

1120. Laminating glue layer, rearview mirror and glass substrate: same as step 1010 of example 10.

1130. Edge sealing with a suitable sealant: the same as in example 1.

In some embodiments, such as the structure shown in FIG. 24, the glass substrate and the mirror have a thickness of about 0.5mm to about 1.8mm, the PVB/EVA adhesive layer has a thickness of about 0.05 mm to about 0.5mm, and the ECD has a thickness of about 0.1mm to about 1 mm.

In some embodiments, the disclosed methods can produce all solid state flexible film ECDs. The electrochromic layer and the ion storage layer are deposited on a flexible plastic substrate to form a thin film. The electrolyte precursor is coated on the surface of any one of the films. Another thin film is then overlaid on the electrolyte precursor to form a stacked structural assembly. The stack is placed under UV light or heated at 80-120 ℃ to induce cross-linking of the electrolyte precursors to form a solid electrolyte, thereby bonding the electrochromic layer and the ion storage layer together. Preassembled film ECDs are readily applied to glass surfaces of varying sizes and curvatures. In addition, the ECDs of the present invention are lighter in weight and do not require cumbersome sealing as compared to conventional glass ECDs that employ liquid or gel electrolytes.

In order to overcome the disadvantages of the conventional ECDs, the present invention discloses a new structure of an electrochromic rearview mirror using a thin film ECD. In such a thin film ECD, an electrochromic layer and an ion storage layer are both prepared on a flexible substrate (e.g., PET) by a high throughput process (e.g., roll-to-roll), and an electrolyte precursor is sandwiched therebetween, and the electrochromic layer, the electrolyte precursor, and the ion storage layer are stacked. And crosslinking the electrolyte precursor by ultraviolet irradiation or heating to form a solid electrolyte, and bonding the electrochromic layer and the ion storage layer together to form the preassembled thin-film device.

In some embodiments, the electrochromic layer and the ion storage layer are coated (e.g., spray coated, spin coated, slot-and-squeeze coated, etc. coating methods now known or developed in the future) on a flexible ITO/PET, and then the electrolyte precursor is sandwiched between the electrochromic layer and the ion storage layer at 20-100 ℃ and 0.01-5MPa at 0.01-0Rolling at a speed of 1-5 m/min. The roller used in the rolling process may use rubber, stainless steel, ceramic, aluminum, or any other material that can withstand a high temperature of 200 c and a high pressure of 10 MPa. The passing energy range of the electrolyte precursor clamped in the thin film is 50-10000mJ cm^-2Or a high temperature of 80-120 ℃. And the electrolyte is crosslinked to form a solid electrolyte, and the electrochromic layer and the ion storage layer are bonded together, so that the all-solid-state thin film electrochromic device is formed. Such a preassembled flexible solid film ECD may be conveniently applied to the manufacture of other window devices, as well as to the retrofitting of conventional eyewear into flat/curved electrochromic smart eyewear.

In some embodiments, the electrochromic layer may be any of the following materials: tungsten trioxide (WO)₃) Polydecyl viologen and its derivatives, polyaniline and its derivatives, various electrochromic conjugated polymers or copolymers containing a certain proportion of acceptor units; the electrochromic conjugated polymer comprises one or a combination of at least two of polypyrrole and derivatives thereof, polythiophene and derivatives thereof, poly (3,4-ethylenedioxythiophene) and derivatives thereof, poly (propylenedioxythiophene) and derivatives thereof, polyfuran and derivatives thereof, polyfluorene and derivatives thereof, polycarbazole and derivatives thereof and copolymers thereof; such acceptor unit-containing copolymers include, for example, one or a combination of at least two of benzothiadiazole, benzoselenadiazole, benzoxazole, benzotriazole, benzimidazole, quinoxaline, and pyrrolopyrroledione, as well as other compounds now known or later developed. The electrochromic layer has a thickness in the range of 1-1500 nm. The ion storage layer may be a nitrile based radical polymer, NiO_xPEDOT, etc., in the thickness range of 1-1000 nm.

The technical scheme of the invention provides a simple method for manufacturing a plane/curved surface anti-glare rearview mirror comprising a solid flexible thin film ECD. The all-solid ECD is safer than conventional materials and packaging methods because it does not leak when the glass is broken. The explosion-proof performance can be further improved by the transparent optical adhesive glue. In addition, the all-solid-state ECDs and the process for manufacturing the same make it possible to use thinner glass substrates and mirrors to reduce the weight of products.

The technical scheme of the invention is beneficial to the mass production of the anti-glare rearview mirrors, is beneficial to reducing the cost, and can greatly improve the productivity and the product yield.

In addition to the anti-glare rearview mirror disclosed in the present invention, the pre-assembled flexible solid state film ECD can be conveniently applied to manufacture other window devices, and to modify conventional eyeglasses into flat/curved electrochromic smart eyeglasses.

The foregoing description of the invention has been presented for purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The scope of the present invention should not be limited by any of the above-described exemplary embodiments. Many modifications and variations will be apparent to those skilled in the art, including any relevant combinations of the disclosed features. The embodiments were chosen and described in order to best explain the principles of the invention and its practical applications, to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the following claims and their equivalents.