Electrochromic material, electrochromic composition and electrochromic device

Abstract

The invention provides an electrochromic material, an electrochromic composition and an electrochromic device, and relates to the technical field of chemical materials. The electrochromic material has a viologen unit with electrochemical activity, the viologen unit is partially reduced under a negative voltage, the charge density is increased, fluorane containing different substituent groups is subjected to a ring closing reaction, and the electrochromic material is changed into a ring-closed colorless state in 35 ms from different colors shown by fluorane containing different substituent groups under the condition that a negative voltage of-1.8 V is applied to the electrochromic material. A standard electron transfer rate constant of a reaction of the viologen unit on the surface of an electrode is very large, the viologen unit is connected with a fluorane part, electrons can be further rapidly transferred to the fluorane part, the fast color changing speed is guaranteed, the electrochemical active viologen unit has very good oxidation reduction cycle stability, and the electrochemical activity of the viologen unit is improved. Therefore, the excellent cycling stability of the whole electrochromic material is ensured, and after 1000 times of cycling, the absorbance change attenuation can be less than 10%.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical materials, and in particular to an electrochromic material, an electrochromic composition and an electrochromic device. Background Art

[0002] Some electrochemically active organic molecules or groups have weak acidity before electrochemical oxidation, but can reversibly release protons after electrochemical oxidation, significantly enhancing the acidity of the system. These substances are called electroacids.

[0003] The electroacid system is the behavior of small organic molecules. The electroacid molecule and the acid-responsive molecule are the same or two different molecules. When the electroacid is oxidized, the proton transfer is from the electroacid molecule to the acid-responsive molecule, or from the electroacid group on the organic small molecule to the acid-responsive group. When the oxidized electroacid is reduced, the proton returns from the acid-responsive molecule to the electroacid molecule, or is transferred from the acid-responsive group on the organic small molecule to the electroacid group. The acceptance and giving of protons by acid-responsive molecules or groups will cause their color to change. After the electric stimulus causes the organic small molecules to be colored, the organic small molecules will diffuse away from the electrode, causing the color of the device to decay. Since the electroacid molecule is far away from the acid-responsive molecule, the proton transfer distance is long, and the electrochromic device has a slower response speed; when the reverse voltage is applied, the coloring molecules or electroacid molecules diffuse away from the electrode, causing the device to fade slowly. Summary of the invention

[0004] The problem solved by the present invention is how to solve the problem of slow response speed of electrochromic devices.

[0005] In order to solve the above problems, the present invention provides an electrochromic material, an electrochromic composition and an electrochromic device.

[0006] In a first aspect, the present invention provides an electrochromic material, the chemical formula of which is any one of the following formulas I, II, III or IV:

[0007]

[0008] Wherein, Y is an O atom, a S atom or Si(CH 3 ) 2 ; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 are any one of H, halogen, C1-C24 alkyl, C1-C24 substituted alkyl, hydroxy, C1-C24 alkoxy, amino, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 groups containing both aromatic rings and alkanes; M- and L - It is Cl - Br - ,I - PF 6 - , BF 4 - Any one of .

[0009] In a second aspect, the present invention provides an electrochromic composition, comprising an electrolyte and the electrochromic material as described above, wherein the molar ratio of the electrochromic material to the electrolyte is 0.001-1000.

[0010] Optionally, the electrolyte is any one of inorganic or organic metal salts containing metal ions, tetraalkyl quaternary ammonium salts or ionic liquids; the inorganic or organic metal salts containing metal ions are one or any combination of Li, Na, K, Rb, Cs, Cu, and Ag salts.

[0011] Optionally, the ionic liquid is butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tributylmethyldibutylammonium phosphate, tributylmethylammonium chloride, tributylmethylmethylammonium carbonate, triethylmethyldibutylammonium phosphate, tetraethylammonium trifluoromethanesulfonate, trioctylmethylammonium hydrogen sulfate, ethyldimethylpropylammonium bis(trifluoromethanesulfonyl)imide, diethylmethyl-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium heptadecafluorooctanesulfonate, tetrabutylammonium nitrite, tetrabutylammonium hydroxide, tetrabutylammonium methanesulfonate, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium succinimide, tetrahexylammonium hydrogen sulfate, tetrahexylammonium iodide, tetraheptylammonium chloride, tetraheptylammonium bromide, tetra-n-butylammonium triiodide, tetrahexyl tetrafluoroborate ammonium, tetrachlorododecyl ammonium, tetrabromododecyl ammonium, tetramethylammonium hydroxide, tetradecyl ammonium bromide, tetraoctylammonium chloride, methyltributylammonium methyl sulfate, methyltri(octadecyl)ammonium bromide, methyltrioctylammonium thiosalicylate, methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, 2-hydroxyethyl-trimethylammonium L-(+)-lactate, 2-hydroxy-N,N-di(2-hydroxyethyl)-N-methylethammonium methyl sulfate, benzyldimethyltetradecylammonium chloride, tetrabutylammonium benzoate, tetrabutylammonium thiophenol, choline acetate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridinium tetrafluoroborate , 1-butyl-4-methylpyridinium iodide, 1-ethylpyridinium tetrafluoroborate, 1-(3-cyanopropyl)pyridinium chloride, 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 4-(3-butyl-1-imidazole)-1-butane sulfonate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3- Methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium hydrogen carbonate, 1-butyl-3-methylimidazolium dibutyl phosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium toluenesulfonate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-Trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium L-(+)-lactate, 1-ethyl-3-methylimidazolium dibutyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1- Ethyl-3-methylimidazolinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethylsulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium p-toluenesulfonyl salt, 1-ethyl-3- Methyl imidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1,3-diethoxyimidazolium hexafluorophosphate, 1,3-diethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methylate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphine, 1,3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium methylsulfate, 1,3-dimethoxyimidazolium hexafluorophosphate, 1,3-dimethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethoxy-2-methylimidazolium hexafluorophosphate, 1,3-dimethoxy-2-methylimidazolium bis(trifluoromethylsulfonyl)imide imide, 1,3-dihydroxy-2-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dihydroxyimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium iodide, 1,3-bis(3-cyanopropyl)imidazolium chloride, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1,3-bis(cyanomethyl)imidazolium chloride, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-2,3-Dimethylimidazolium, 1-ethyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-(3-cyanopropyl)-3-imidazolium dicyanamide, 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, 1-(3-cyanopropyl)-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-propylimidazolium methyl carbonate, 1-methyl-3-propylimidazolium iodide, 1-methyl-3-vinylimidazole methyl carbonate, 1-methylimidazolium hydrogen sulfate, 1- Methylimidazolium chloride, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium chloride, 1-decyl-3-methylimidazolium tetrafluoroborate, decylmethylimidazolium chloride, 1-hexyl-3-methylimidazolium iodide, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl- 3-Methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium hydrogen sulfate, 1-methylimidazolium chloride, tributylmethylphosphine dibutyl phosphate, tributylmethylphosphine methylsulfate, triethylmethylphosphine dibutyl phosphate, trihexyltetradecylphosphine bromide, trihexyltetradecylphosphine chloride, trihexyltetradecylphosphine decanoate, trihexyl (tetradecyl) phosphine dicyanamide, trihexyltetradecylphosphine bis (trifluoromethylsulfonyl) amide, trihexyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphite, 3-(triphenylphosphino)propane-1-toluenesulfonyl, 3-(triphenylphosphino)propane-1-sulfonate, tetrabutylphosphine tetrafluoroborate, tetrabutylphosphine p-toluenesulfonate, tetrabutylphosphine methanesulfonate, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine dinitrile amine salt, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine tetrafluoroborate, 1-butyl-1-methylpyrrolidine chloride, 1-butyl-1-methylpyrrolidine bromide, 1- Any one of butyl-1-methylpyrrolidinium iodide, 1-butyl-1-methylpyrrolidinium methyl carbonate, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-methyl-1-ethylpyrrolidinium hexafluorophosphate, 1-methyl-1-ethylpyrrolidinium bromide, triethylsulfonium bis(trifluoromethylsulfonyl)imide, cyclopropyldiphenylsulfonium tetrafluoroborate, 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-1-methylpiperidinium hexafluorophosphate, 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 4-ethyl-4-methylmorpholine methyl carbonate, and C 4-C 60 ionic liquids containing at least one S, N, or P heteroatom.

[0012] In a third aspect, the present invention provides an electrochromic device, comprising a first electrode, an electrochromic medium, an ion exchange membrane, an auxiliary medium and a second electrode, wherein the electrochromic medium is composed of the electrochromic composition as described above dispersed in a liquid medium or a solid medium.

[0013] Optionally, the electrode material used in the first electrode and the second electrode is a combination of a first material and a second material, wherein the first material is any one of gold, silver, copper, mercury, platinum, palladium, tungsten, aluminum, zinc, zinc oxide, and indium oxide, and the second material is any one of tin oxide composite, tungsten carbide, nickel carbide, graphite, graphene, and carbon nanotube electrode materials.

[0014] Optionally, the ion exchange membrane is any one of a proton exchange membrane, a lithium ion conductive membrane, a cation exchange membrane, an anion exchange membrane, a liquid medium containing an electrolyte, or a solid medium.

[0015] Optionally, the auxiliary medium is a liquid medium or a solid medium containing an electrolyte, or a liquid medium or a solid medium containing a substance having an oxidizing property and an electrolyte mixed therein.

[0016] Optionally, the substance having oxidizing properties is any one of phenolic compounds, amine compounds, TEMPO compounds, metal salts, and metal complexes;

[0017] The liquid medium is a solvent or an ionic liquid, and the solid medium is a high molecular polymer.

[0018] Optionally, the solvent is any combination of water, C1-C 18 alcohols, C 3-C 24 ethers containing at least one oxygen atom, C 3-C 24 sulfides containing at least one sulfur atom, C 2-C 18 sulfoxides, C 2-C 18 sulfones, C 3-C 24 ketones, C1-C 18 acids, C1-C 18 sulfonic acids, C 2-C 18 esters, C1-C 18 amides, C1-C 18 alkanes, C1-C 18 alkenes, C1-C 18 alkynes, C1-C 18 aromatic hydrocarbons, C 3-C 18 heterocycles containing at least one heteroatom O, S, N, P, alkanes containing at least one halogen atom, and aromatic hydrocarbons containing at least one halogen atom;

[0019] The high molecular polymer is any combination of polystyrene, polypropylene, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polypentyl acrylate, polyisopentyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polypentyl methacrylate, polyisopentyl methacrylate, polyhexyl methacrylate, polyethylene glycol, polyvinyl alcohol, polyurethane, polyethylene, polycarbonate, polyamide, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl acetate, polysilicone, polyacrylonitrile, polychlorotrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, and polydimethylsilicate.

[0020] The electrochromic material, electrochromic composition and electrochromic device of the present invention have the following beneficial effects: the electrochemically active viologen unit part in the electrochromic material is reduced under negative voltage, the charge density increases, and the fluoran containing different substituents undergoes a ring-closing reaction. The different colors exhibited by the fluoran with different substituents in the electrochromic material change to a ring-closing colorless state in 35ms when a negative voltage of -1.8V is applied. The electrochemically active viologen unit in the electrochromic material has a large standard electron transfer rate constant for its own reaction on the electrode surface. Connecting it with the fluoran part can quickly transfer electrons to the fluoran part, thereby ensuring a fast color change speed. The electrochemically active viologen unit itself has good redox cycle stability, thereby ensuring the excellent cycle stability of the overall electrochromic material. After 1000 cycles, the absorbance change attenuation can be less than 10%. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the change of absorbance over time in the electrochemical and ultraviolet spectroscopy combined test of the electrochromic device of Example 1;

[0022] Figure 2 is the compound of formula Ⅰ-1 in Example 1 1 H NMR spectrum (DMSO-d6 as solvent, 400 MHz frequency);

[0023] Figure 3 is the compound of formula Ⅰ-1 in Example 1 13 C NMR spectrum (DMSO-d6 as solvent, 101 MHz frequency);

[0024] Figure 4 is a curve diagram of the fading efficiency and coloring efficiency of the electrochromic device prepared by Formula I-1 in Example 1;

[0025] Figure 5 is a graph of the fading time and coloring time of the electrochromic device prepared by Formula I-1 in Example 1;

[0026] Figure 6 In Example 1, the formula Ⅰ-1, MV 2+ , Schematic diagram of the coloring time comparison of the electrochromic device prepared by Rhodamine B;

[0027] Figure 7 is the compound of formula Ⅰ-2 in Example 2 1 H NMR spectrum (DMSO-d6 as solvent, 400 MHz frequency);

[0028] Figure 8 FIG. 4 is a graph showing the UV-visible absorption spectra of M5 at different voltages according to an embodiment of the present invention. DETAILED DESCRIPTION

[0029] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific embodiments of the present invention are described in detail below in conjunction with the accompanying drawings. Although certain embodiments of the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be interpreted as being limited to the embodiments described herein. On the contrary, these embodiments are provided to provide a more thorough and complete understanding of the present invention. It should be understood that the drawings and embodiments of the present invention are only for exemplary purposes and are not intended to limit the scope of protection of the present invention.

[0030] Unless otherwise defined, all technical and scientific terms used in this application have the same meanings as those commonly understood by those skilled in the art to which this application belongs; the terms used in the specification of this application are only for the purpose of describing specific implementation methods and are not intended to limit this application;

[0031] The term "including" and its variations used in this article are open inclusions, that is, "including but not limited to"; the term "based on" is "based at least in part on"; the term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one other embodiment"; the term "some embodiments" means "at least some embodiments"; the term "optionally" means "optional embodiments". The relevant definitions of other terms will be given in the following description. It should be noted that the concepts of "first" and "second" mentioned in the present invention are used to distinguish different objects, rather than to describe a specific order or a primary and secondary relationship. In addition, the terms "first" and "second" are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of this application, unless otherwise specified, the meaning of "multiple" is two or more.

[0032] In view of the problems existing in the above-mentioned related technologies, this embodiment provides an electrochromic material, an electrochromic composition and an electrochromic device.

[0033] An electrochromic material provided in an embodiment of the present invention has a chemical formula of any one of the following formulas I, II, III or IV:

[0034]

[0035] Wherein, Y is an O atom, a S atom or Si(CH 3 ) 2 ; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19 are any one of H, halogen, C1-C24 alkyl, C1-C24 substituted alkyl, hydroxyl, C1-C24 alkoxy, amino, C1-C24 alkylamino, C6-C24 aryl, or a C7-C24 group containing both an aromatic ring and an alkane; M - and L - It is Cl - Br - ,I - PF 6 - or BF 4 - Any one of .

[0036] The electrochromic mechanism of Formula I to Formula IV is as follows: the electrochemically active viologen unit in the electrochromic material is partially reduced under negative voltage, the charge density increases, and the fluoran containing different substituents undergoes a ring-closing reaction, and the electrochromic material changes from the different colors exhibited by the fluoran with different substituents to a ring-closing colorless state. The electrochemically active viologen unit in the electrochromic material has a large standard electron transfer rate constant for its own reaction on the electrode surface. Connecting it with the fluoran part can further enable electrons to be quickly transferred to the fluoran part, thereby ensuring a fast color change speed. The electrochemically active viologen unit itself has good redox cycle stability, thereby ensuring the excellent cycle stability of the overall electrochromic material.

[0037]

[0038] An embodiment of the present invention provides an electrochromic composition, comprising an electrolyte and the electrochromic material as described above, wherein the molar ratio of the electrochromic material to the electrolyte is 0.001-1000.

[0039] Optionally, the electrolyte is any one of inorganic or organic metal salts containing metal ions, tetraalkyl quaternary ammonium salts or ionic liquids; the inorganic or organic metal salts containing metal ions are one or any combination of Li, Na, K, Rb, Cs, Cu or Ag salts.

[0040] Optionally, the ionic liquid is butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tributylmethyldibutylammonium phosphate, tributylmethylammonium chloride, tributylmethylmethylammonium carbonate, triethylmethyldibutylammonium phosphate, tetraethylammonium trifluoromethanesulfonate, trioctylmethylammonium hydrogen sulfate, ethyldimethylpropylammonium bis(trifluoromethanesulfonyl)imide, diethylmethyl-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium heptadecafluorooctanesulfonate, tetrabutylammonium nitrite, tetrabutylammonium hydroxide, tetrabutylammonium methanesulfonate, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium succinimide, tetrahexylammonium hydrogen sulfate, tetrahexylammonium iodide, tetraheptylammonium chloride, tetraheptylammonium bromide, tetra-n-butylammonium triiodide, tetrahexyl tetrafluoroborate ammonium, tetrachlorododecyl ammonium, tetrabromododecyl ammonium, tetramethylammonium hydroxide, tetradecyl ammonium bromide, tetraoctylammonium chloride, methyltributylammonium methyl sulfate, methyltri(octadecyl)ammonium bromide, methyltrioctylammonium thiosalicylate, methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, 2-hydroxyethyl-trimethylammonium L-(+)-lactate, 2-hydroxy-N,N-di(2-hydroxyethyl)-N-methylethammonium methyl sulfate, benzyldimethyltetradecylammonium chloride, tetrabutylammonium benzoate, tetrabutylammonium thiophenol, choline acetate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridinium tetrafluoroborate , 1-butyl-4-methylpyridinium iodide, 1-ethylpyridinium tetrafluoroborate, 1-(3-cyanopropyl)pyridinium chloride, 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 4-(3-butyl-1-imidazole)-1-butane sulfonate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3- Methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium nitrate, 1-butyl-3-methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium octyl sulfate, 1-butyl-3-methylimidazolium iodide, 1-butyl-3-methylimidazolium hydrogen carbonate, 1-butyl-3-methylimidazolium dibutyl phosphate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrachloroaluminate, 1-butyl-3-methylimidazolium toluenesulfonate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-Trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium L-(+)-lactate, 1-ethyl-3-methylimidazolium dibutyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1- Ethyl-3-methylimidazolinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethylsulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium p-toluenesulfonyl salt, 1-ethyl-3- Methyl imidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1,3-diethoxyimidazolium hexafluorophosphate, 1,3-diethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methylate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphine, 1,3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium methylsulfate, 1,3-dimethoxyimidazolium hexafluorophosphate, 1,3-dimethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethoxy-2-methylimidazolium hexafluorophosphate, 1,3-dimethoxy-2-methylimidazolium bis(trifluoromethylsulfonyl)imide imide, 1,3-dihydroxy-2-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dihydroxyimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium iodide, 1,3-bis(3-cyanopropyl)imidazolium chloride, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1,3-bis(cyanomethyl)imidazolium chloride, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-2,3-Dimethylimidazolium, 1-ethyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-(3-cyanopropyl)-3-imidazolium dicyanamide, 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, 1-(3-cyanopropyl)-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-propylimidazolium methyl carbonate, 1-methyl-3-propylimidazolium iodide, 1-methyl-3-vinylimidazole methyl carbonate, 1-methylimidazolium hydrogen sulfate, 1- Methylimidazolium chloride, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium chloride, 1-decyl-3-methylimidazolium tetrafluoroborate, decylmethylimidazolium chloride, 1-hexyl-3-methylimidazolium iodide, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl- 3-Methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium hydrogen sulfate, 1-methylimidazolium chloride, tributylmethylphosphine dibutyl phosphate, tributylmethylphosphine methylsulfate, triethylmethylphosphine dibutyl phosphate, trihexyltetradecylphosphine bromide, trihexyltetradecylphosphine chloride, trihexyltetradecylphosphine decanoate, trihexyl (tetradecyl) phosphine dicyanamide, trihexyltetradecylphosphine bis (trifluoromethylsulfonyl) amide, trihexyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphite, 3-(triphenylphosphino)propane-1-toluenesulfonyl, 3-(triphenylphosphino)propane-1-sulfonate, tetrabutylphosphine tetrafluoroborate, tetrabutylphosphine p-toluenesulfonate, tetrabutylphosphine methanesulfonate, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine dinitrile amine salt, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine tetrafluoroborate, 1-butyl-1-methylpyrrolidine chloride, 1-butyl-1-methylpyrrolidine bromide, 1- Any one of butyl-1-methylpyrrolidinium iodide, 1-butyl-1-methylpyrrolidinium methyl carbonate, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-methyl-1-ethylpyrrolidinium hexafluorophosphate, 1-methyl-1-ethylpyrrolidinium bromide, triethylsulfonium bis(trifluoromethylsulfonyl)imide, cyclopropyldiphenylsulfonium tetrafluoroborate, 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-1-methylpiperidinium hexafluorophosphate, 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 4-ethyl-4-methylmorpholine methyl carbonate, and C 4-C 60 ionic liquids containing at least one S, N, or P heteroatom.

[0041] An embodiment of the present invention provides an electrochromic device, which is composed of a first electrode, an electrochromic medium, an ion exchange membrane, an auxiliary medium and a second electrode, wherein the electrochromic medium is composed of the electrochromic composition as described above dispersed in a liquid medium or a solid medium.

[0042] Optionally, the electrode material used in the first electrode and the second electrode is a combination of a first material and a second material, wherein the first material is gold, silver, copper, mercury, platinum, palladium, tungsten, aluminum, zinc, zinc oxide or indium oxide, and the second material is a tin oxide composite, tungsten carbide, nickel carbide, graphite, graphene or carbon nanotube electrode material.

[0043] Optionally, the ion exchange membrane is any one of a proton exchange membrane, a lithium ion conductive membrane, a cation exchange membrane, an anion exchange membrane, or a liquid medium or a solid medium containing an electrolyte.

[0044] The thickness of the ion exchange membrane can be 20nm-500μm. The increase in thickness makes the electrochromic bistable effect of the electrochromic device better. If the ion exchange membrane is too thin, the ion exchange membrane material is easy to diffuse and combine with the color-changing layer material, affecting the bistable maintenance effect, and it is easy to cause the device to break down when voltage is applied; if the ion exchange membrane is too thick, the distance of ion migration becomes longer, and the response speed of the electrochromic device is poor. When the thickness of the ion exchange membrane is less than 20nm, the electrochromic device has no bistable maintenance effect, and the maximum voltage of the electrochromic device can only be applied to 0.5V; when the thickness of the ion exchange membrane is greater than 500μm, the electrochromic device fades in 30 minutes, resulting in poor response speed of the electrochromic device.

[0045] Optionally, the auxiliary medium is a liquid medium or a solid medium containing an electrolyte, or a liquid medium or a solid medium containing a substance having an oxidizing property and an electrolyte mixed therein.

[0046] Optionally, the substance having oxidizing properties is a phenolic compound, an amine compound, a TEMPO compound, a metal salt or a metal complex;

[0047] The liquid medium is a solvent or an ionic liquid, and the solid medium is a high molecular polymer.

[0048] Optionally, the solvent is any combination of water, C1-C 18 alcohols, C 3-C 24 ethers containing at least one oxygen atom, C 3-C 24 sulfides containing at least one sulfur atom, C 2-C 18 sulfoxides, C 2-C 18 sulfones, C 3-C 24 ketones, C1-C 18 acids, C1-C 18 sulfonic acids, C 2-C 18 esters, C1-C 18 amides, C1-C 18 alkanes, C1-C 18 alkenes, C1-C 18 alkynes, C1-C 18 aromatic hydrocarbons, C 3-C 18 heterocycles containing at least one heteroatom O, S, N, P, alkanes containing at least one halogen atom, and aromatic hydrocarbons containing at least one halogen atom;

[0049] The high molecular polymer is any combination of polystyrene, polypropylene, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polypentyl acrylate, polyisopentyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polypentyl methacrylate, polyisopentyl methacrylate, polyhexyl methacrylate, polyethylene glycol, polyvinyl alcohol, polyurethane, polyethylene, polycarbonate, polyamide, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl acetate, polysilicone, polyacrylonitrile, polychlorotrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, and polydimethylsilicate.

[0050] The present invention is further described below in conjunction with specific embodiments.

[0051] Example 1

[0052] The following synthesis equation is used to synthesize the electrochromic material formula I-1

[0053]

[0054]

[0055] Specifically, M1 molecule, i.e. 2,3-dimethyl 4-bromopyridine (1.86g, 10mmol), 4-pyridine boronic acid (1.35g, 11.0mmol) and tetrakis(triphenylphosphine)palladium (0.58g, 0.5mmol) were added to a 100mL double-necked flask, and 10mL sodium bicarbonate aqueous solution (2mol / L) and 10mL toluene were added in sequence, and then 10mL anhydrous ethanol was added to dissolve it. Under nitrogen protection, the oil bath was heated and stirred at 90°C for 48h. After the reaction was completed, the reaction system was naturally cooled to room temperature, and the obtained product was dissolved in 20mL ethyl acetate and then washed with 40mL saturated ammonium chloride aqueous solution. 40mL ethyl acetate was added for extraction, liquid separation, and extraction was repeated three times. The organic phases were combined, and anhydrous sodium sulfate solid was added to dry for 20 minutes. Column chromatography was performed using pure ethyl acetate solvent as an eluent to separate and purify the target product molecule. The obtained white solid product, i.e. M2 molecule, had a yield of 90%. Add M2 molecule (4.61g, 25mmol) and 50mL deionized water to a 100mL round-bottom flask. Heat the reaction to 100℃ and add potassium permanganate (23.0g, 250mmol) in 5 times within 3 hours. After the reaction is completed, the reaction system is cooled to room temperature naturally, solid impurities are removed by filtration using diatomaceous earth, and the pH value of the filtrate is adjusted to 3-4 with 6mol / L hydrochloric acid. The filtrate is dried by rotary evaporation to obtain a white crude product M3. Add crude product M3 (25mmol), 3-diethylaminophenol (8.25g, 50mmol), and trifluoromethanesulfonic acid (3.75g, 25mmol) to a 100mL round-bottom flask, and then add 50mL chlorobenzene. Heat and stir the reaction in an oil bath at 135℃ for 12h. After the reaction is completed, the reaction system is cooled to room temperature naturally, the solvent is removed by rotary evaporation, the crude product is dissolved in dichloromethane, and washed three times with saturated sodium bicarbonate solution. Combine the organic phases, add anhydrous sodium sulfate solid and dry for 20 minutes. Use dichloromethane / methanol solvent as eluent for column chromatography to separate and purify the target product molecule. The obtained red solid product is the intermediate product M4 molecule, with a yield of 5%. Add M4 molecule (520mg, 1.0mmol), iodomethane (1.42g, 10mmol), and 50mL of acetonitrile into a 100mL round-bottom flask. Heat and stir in an oil bath at 40℃ for 4d. After the reaction is completed, allow the reaction system to cool naturally to room temperature, use a rotary evaporator to remove the solvent, dissolve the crude product in dichloromethane, and wash with saturated potassium hexafluorophosphate solution. Add anhydrous sodium sulfate solid to the organic phase and dry for 20 minutes. Use dichloromethane / methanol solvent as eluent for column chromatography to separate and purify the target product molecule. The obtained red solid product is product M5, with a yield of 50%, and M5 is used for mechanism proof. M4 molecule (520 mg, 1.0 mmol), 3-bromo-1-propanol (700 mg, 5 mmol) and 50 mL of acetonitrile were added into a 100 mL round-bottom flask.The reaction was stirred in an oil bath at 80°C for 4 days. After the reaction was completed, the reaction system was cooled to room temperature naturally, the solvent was removed by a rotary evaporator, the crude product was dissolved in dichloromethane, and washed with a saturated potassium hexafluorophosphate solution. Anhydrous sodium sulfate solid was added to the organic phase and dried for 20 minutes. Column chromatography was performed using dichloromethane / methanol solvent as an eluent to separate and purify the target product molecule. The resulting red solid product M6 had a yield of 10%. M6 molecule (145 mg, 0.2 mmol), iodomethane (280 mg, 2 mmol), and 20 mL of acetonitrile were added to a 50 mL round-bottom flask. The reaction was stirred in an oil bath at 40°C for 4 days. After the reaction was completed, the reaction system was cooled to room temperature naturally, the solvent was removed by a rotary evaporator, the crude product was dissolved in dichloromethane, and washed with a saturated potassium hexafluorophosphate solution. Anhydrous sodium sulfate solid was added to the organic phase and dried for 20 minutes. Column chromatography was performed using dichloromethane / methanol solvent as an eluent to separate and purify the target product molecule. The obtained red solid product M7 has a yield of 50%. Add M7 molecule (88.5 mg, 0.1 mmol), methacryloyl chloride (20.9 mg, 0.2 mmol), triethylamine (20.2 mg, 0.2 mmol), and 10 mL of dichloromethane into a 50 mL round-bottom flask. Stir the reaction at 25 ° C for 6 hours. After the reaction is completed, wash with saturated potassium hexafluorophosphate solution. Add anhydrous sodium sulfate solid to the organic phase and dry for 20 minutes. Use dichloromethane / methanol solvent as an eluent for column chromatography to separate and purify the target product molecule. The obtained red solid product formula Ⅰ-1 has a yield of 77%.

[0056] The color change mechanism of M5 is demonstrated by the mechanism: When a voltage of -1.0V is applied to the solution of M5 molecules, the molecular structure undergoes the following changes, and its UV-visible absorption spectrum undergoes obvious changes; when a positive voltage of +0.8V is applied to it, its molecular structure returns to its initial state, and its UV-visible absorption spectrum returns to its initial state, such as Figure 8 shown.

[0057]

[0058] Formula I-1 is used as an electrochromic material, tetrabutylammonium hexafluorophosphate is used as an electrolyte, and the two are mixed as an electrochromic composition, and acetonitrile is used as a solvent. Electrochromic medium preparation: 1mmol of tetrabutylammonium hexafluorophosphate as an electrolyte, 1g of polymethyl methacrylate as a film-forming medium, 20mg of formula I-1, and 10mL of acetonitrile as a solvent.

[0059] The invention is composed of a first electrode, an electrochromic medium, an ion exchange membrane, an auxiliary medium and a second electrode, wherein the electrochromic medium is composed of the electrochromic composition according to any one of claims 2 to 4 dispersed in a liquid medium or a solid medium.

[0060] Preparation of electrochromic device: The first electrode and the second electrode are both ITO electrodes, the auxiliary medium is a TEMPO compound, the ion exchange membrane is a liquid medium containing electrolyte, polymethyl methacrylate (PMMA) gel electrolyte is selected, and the ion exchange membrane acts as an ion transport layer. The above electrochromic medium is spin-coated onto a clean ITO electrode, and then assembled into an electrochromic device. Under a negative voltage of -1.8V, the electrochromic device changes from purple-red to colorless and transparent; under a positive voltage of +1.6V, the colorless and transparent changes to purple-red again. Figure 4 As shown in Figure 2, the fading efficiency and coloring efficiency of the electrochromic device are both high. Figure 1 As shown, the electrochemical and ultraviolet spectroscopic tests are combined, and the absorption wavelength selected for detection is the optimal wavelength of 575nm when the substance is in a colored state. Figure 5 As shown in the figure, the horizontal axis is time and the vertical axis is absorbance. After applying a negative voltage of -1.8V for 35ms, the transmittance of the device changes from purple-red to colorless and transparent, and the absorbance changes by 0.1, with a fast color change speed. Under a positive voltage of +1.6 for 65ms, the colorless and transparent state changes to purple-red again, with high coloring efficiency. Figure 1 As shown, after 1000 cycles, the absorbance change decays by less than 10%, indicating that the device has good cycle reversibility and cycle stability.

[0061] Figure 2 The H NMR spectrum of Formula Ⅰ-1 ( 1 H NMR) spectrum (400 MHz, DMSO-d 6 ), the molecule of formula Ⅰ-1 is dissolved in the deuterated reagent DMSO-d6 molecule, the instrument frequency is 400MHz, and the molecular structure of formula Ⅰ-1 is confirmed, Figure 3 The carbon NMR spectrum of formula Ⅰ-1 ( 13 C NMR) spectrum (101 MHz, DMSO-d 6 ), the molecule of formula Ⅰ-1 is dissolved in the deuterated reagent DMSO-d6 molecule, the instrument frequency is 101 MHz, and the molecular structure of formula Ⅰ-1 is confirmed.

[0062] The formula Ⅰ-1, methyl viologen (MV 2+ ), the electrochromic device prepared by Rhodamine B fluorescent dye has a coloring time of +1.6 at a positive voltage, such as Figure 6 As shown, the electrochromic device prepared by Formula Ⅰ-1 has a coloring time of only 65ms, the fastest coloring speed, and high coloring efficiency.

[0063] Methyl viologen (MV 2+ ) has the following molecular structure:

[0064]

[0065] Example 2

[0066] The following synthesis equation is used to synthesize the electrochromic material formula I-2

[0067]

[0068] The synthesis process is similar to that of the synthesis of Formula Ⅰ-1 in Example 1 to obtain the final product of Formula Ⅰ-2.

[0069] Formula I-2 is used as an electrochromic material, tetrabutylammonium hexafluorophosphate is used as an electrolyte, and the two are mixed as an electrochromic composition, and acetonitrile is used as a solvent. Electrochromic medium preparation: 1mmol of tetrabutylammonium hexafluorophosphate as an electrolyte, 1g of polymethyl methacrylate as a film-forming medium, 20mg of formula I-2, and 10mL of acetonitrile as a solvent.

[0070] Preparation of electrochromic device: The first electrode and the second electrode are both ITO electrodes, the auxiliary medium is a TEMPO compound, the ion exchange membrane is a liquid medium containing electrolyte, polymethyl methacrylate (PMMA) gel electrolyte is selected, and the ion exchange membrane plays the role of ion transport layer. The above electrochromic medium is spin-coated onto a clean ITO electrode, and then assembled into an electrochromic device. Under the condition of negative voltage -1.8V, the electrochromic device changes from blue to colorless and transparent; under positive voltage +1.6V, the colorless and transparent state changes to blue again. After 1000 cycles, the absorbance change decays by less than 10%, indicating that the device has good cycle reversibility and cycle stability.

[0071] Figure 7 The H NMR spectrum of Formula Ⅰ-2 ( 1 H NMR) spectrum (400 MHz, DMSO-d 6 ), the molecule of formula Ⅰ-1 is dissolved in the deuterated reagent DMSO-d6 molecule, and the instrument frequency is 400 MHz, proving the molecular structure of formula Ⅰ-1.

[0072] Example 3

[0073] The following synthesis equation is used to synthesize the electrochromic material formula I-3

[0074]

[0075] The synthesis process is similar to that of the synthesis of Formula Ⅰ-1 in Example 1 to obtain the final product of Formula Ⅰ-3.

[0076] Formula I-3 is used as an electrochromic material, tetrabutylammonium hexafluorophosphate is used as an electrolyte, and the two are mixed as an electrochromic composition, and acetonitrile is used as a solvent. Electrochromic medium preparation: 1mmol of tetrabutylammonium hexafluorophosphate is used as an electrolyte, 1g of polymethyl methacrylate is used as a film-forming medium, 20mg of formula I-3, and 10mL of acetonitrile is used as a solvent.

[0077] Preparation of electrochromic device: The first electrode and the second electrode are both ITO electrodes, the auxiliary medium is a TEMPO compound, the ion exchange membrane is a liquid medium containing electrolyte, and polymethyl methacrylate (PMMA) gel electrolyte is selected. The ion exchange membrane plays the role of ion transport layer. The above electrochromic medium is spin-coated onto a clean ITO electrode, and then assembled into an electrochromic device. Under the condition of negative voltage -1.8V, the electrochromic device changes from yellow to colorless and transparent; under positive voltage +1.6V, the colorless and transparent state changes to yellow again. After 1000 cycles, the absorbance change decays by less than 10%, indicating that the device has good cycle reversibility and cycle stability.

[0078] Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. An electrochromic material, characterized in that: The chemical formula is any one of the following formula I, formula II, formula III or formula IV: Wherein, Y is an O atom, a S atom or Si(CH3)2; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18 and R19 are any one of H, halogen, C1-C24 alkyl, C1-C24 substituted alkyl, hydroxyl, C1-C24 alkoxy, amino, C1-C24 alkylamino, C6-C24 aryl, and C7-C24 group containing both aromatic ring and alkane; M - and L - It is Cl - Br - ,I - PF6 - 、BF4 - Any one of .

2. An electrochromic composition, characterized in that: The invention comprises an electrolyte and the electrochromic material according to claim 1, wherein the molar ratio of the electrochromic material to the electrolyte is 0.001-1000.

3. The electrochromic composition according to claim 2, characterized in that: The electrolyte is any one of inorganic or organic metal salts containing metal ions, tetraalkyl quaternary ammonium salts or ionic liquids; the inorganic or organic metal salts containing metal ions are one or any combination of Li, Na, K, Rb, Cs, Cu, and Ag salts.

4. The electrochromic composition according to claim 3, characterized in that: The ionic liquid is butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tributylmethyldibutylammonium phosphate, tributylmethylammonium chloride, tributylmethylmethylammonium carbonate, triethylmethyldibutylammonium phosphate, tetraethylammonium trifluoromethanesulfonate, trioctylmethylammonium hydrogen sulfate, ethyldimethylpropylammonium bis(trifluoromethanesulfonyl)imide, diethylmethyl-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium heptadecafluorooctanesulfonate, tetrabutylammonium nitrite, tetrabutylammonium hydroxide, tetrabutylammonium methanesulfonate, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium succinimide, tetrahexylammonium hydrogen sulfate, tetrahexylammonium iodide, tetraheptylammonium chloride, tetraheptylammonium bromide, tetra-n-butylammonium triiodide, tetrahexylammonium tetrafluoroborate , dodecyl ammonium tetrachloride, dodecyl ammonium tetrabromide, tetramethyl ammonium hydroxide, tetradecyl ammonium bromide, tetraoctylammonium chloride, methyl tributyl ammonium methyl sulfate, methyl tri(octadecyl) ammonium bromide, methyl trioctyl ammonium thiosalicylate, methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, 2-hydroxyethyl-trimethylammonium L-(+)-lactate, 2-hydroxy-N,N-di(2-hydroxyethyl)-N-methylethammonium methyl sulfate, benzyldimethyltetradecyl ammonium chloride, tetrabutylammonium benzoate, tetrabutylammonium thiophenol, choline acetate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-Butyl-4-methylpyridinium iodide, 1-ethylpyridinium tetrafluoroborate, 1-(3-cyanopropyl)pyridinium chloride, 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 4-(3-butyl-1-imidazole)-1-butane sulfonate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methyl 1-Butyl-3-methylimidazolium chloride, 1-Butyl-3-methylimidazolium bromide, 1-Butyl-3-methylimidazolium methanesulfonate, 1-Butyl-3-methylimidazolium nitrate, 1-Butyl-3-methylimidazolium hydrogen sulfate, 1-Butyl-3-methylimidazolium methyl sulfate, 1-Butyl-3-methylimidazolium octyl sulfate, 1-Butyl-3-methylimidazolium iodide, 1-Butyl-3-methylimidazolium hydrogen carbonate, 1-Butyl-3-methylimidazolium dibutyl phosphate, 1-Butyl-3-methylimidazolium trifluoromethanesulfonate, 1-Butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-methylimidazolium tetrachloroaluminate, 1-Butyl-3-methylimidazolium toluenesulfonate, 1-Butyl-3-methylimidazolium thiocyanate, 1,2,3-Trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium L-(+)-lactate, 1-ethyl-3-methylimidazolium dibutyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1- Ethyl-3-methylimidazolinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethylsulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium p-toluenesulfonyl salt, 1-ethyl-3- Methyl imidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1,3-diethoxyimidazolium hexafluorophosphate, 1,3-diethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methylate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphine, 1,3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium methylsulfate, 1,3-dimethoxyimidazolium hexafluorophosphate, 1,3-dimethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethoxy-2-methylimidazolium hexafluorophosphate, 1,3-dimethoxy-2-methylimidazolium bis(trifluoromethylsulfonyl)imide imide, 1,3-dihydroxy-2-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dihydroxyimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium iodide, 1,3-bis(3-cyanopropyl)imidazolium chloride, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1,3-bis(cyanomethyl)imidazolium chloride, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-2,3-Dimethylimidazolium, 1-ethyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-(3-cyanopropyl)-3-imidazolium dicyanamide, 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, 1-(3-cyanopropyl)-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-propylimidazolium methyl carbonate, 1-methyl-3-propylimidazolium iodide, 1-methyl-3-vinylimidazole methyl carbonate, 1-methylimidazolium hydrogen sulfate, 1- Methylimidazolium chloride, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium chloride, 1-decyl-3-methylimidazolium tetrafluoroborate, decylmethylimidazolium chloride, 1-hexyl-3-methylimidazolium iodide, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl- 3-Methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium hydrogen sulfate, 1-methylimidazolium chloride, tributylmethylphosphine dibutyl phosphate, tributylmethylphosphine methylsulfate, triethylmethylphosphine dibutyl phosphate, trihexyltetradecylphosphine bromide, trihexyltetradecylphosphine chloride, trihexyltetradecylphosphine decanoate, trihexyl (tetradecyl) phosphine dicyanamide, trihexyltetradecylphosphine bis (trifluoromethylsulfonyl) amide, trihexyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphite, 3-(triphenylphosphino)propane-1-toluenesulfonyl, 3-(triphenylphosphino)propane-1-sulfonate, tetrabutylphosphine tetrafluoroborate, tetrabutylphosphine p-toluenesulfonate, tetrabutylphosphine methanesulfonate, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine dinitrile amine salt, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine tetrafluoroborate, 1-butyl-1-methylpyrrolidine chloride, 1-butyl-1-methylpyrrolidine bromide, 1- Any one of butyl-1-methylpyrrolidinium iodide, 1-butyl-1-methylpyrrolidinium methyl carbonate, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-methyl-1-ethylpyrrolidinium hexafluorophosphate, 1-methyl-1-ethylpyrrolidinium bromide, triethylsulfonium bis(trifluoromethylsulfonyl)imide, cyclopropyldiphenylsulfonium tetrafluoroborate, 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-1-methylpiperidinium hexafluorophosphate, 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 4-ethyl-4-methylmorpholine methyl carbonate, and C 4-C 60 ionic liquids containing at least one S, N, or P heteroatom.

5. An electrochromic device, characterized in that: The invention is composed of a first electrode, an electrochromic medium, an ion exchange membrane, an auxiliary medium and a second electrode, wherein the electrochromic medium is composed of the electrochromic composition according to any one of claims 2 to 4 dispersed in a liquid medium or a solid medium.

6. The electrochromic device according to claim 5, characterized in that: The electrode material used in the first electrode and the second electrode is a combination of a first material and a second material, wherein the first material is any one of gold, silver, copper, mercury, platinum, palladium, tungsten, aluminum, zinc, zinc oxide, and indium oxide, and the second material is any one of tin oxide composite, tungsten carbide, nickel carbide, graphite, graphene, and carbon nanotube electrode materials.

7. The electrochromic device according to claim 5, characterized in that: The ion exchange membrane is any one of a proton exchange membrane, a lithium ion conductive membrane, a cation exchange membrane, an anion exchange membrane, a liquid medium containing an electrolyte, or a solid medium.

8. The electrochromic device according to claim 5, characterized in that: The auxiliary medium is a liquid medium or a solid medium containing an electrolyte, or a liquid medium or a solid medium containing a substance having an oxidizing property mixed with the electrolyte.

9. The electrochromic device according to claim 8, characterized in that: The substance with oxidizing properties is any one of phenolic compounds, amine compounds, TEMPO compounds, metal salts, and metal complexes; The liquid medium is a solvent or an ionic liquid, and the solid medium is a high molecular polymer.

10. The electrochromic device according to claim 9, characterized in that: The solvent is any combination of water, C1-C 18 alcohols, C 3-C 24 ethers containing at least one oxygen atom, C 3-C 24 sulfides containing at least one sulfur atom, C 2-C 18 sulfoxides, C 2-C 18 sulfones, C 3-C 24 ketones, C1-C 18 acids, C1-C 18 sulfonic acids, C 2-C 18 esters, C1-C 18 amides, C1-C 18 alkanes, C1-C 18 alkenes, C1-C 18 alkynes, C1-C 18 aromatic hydrocarbons, C 3-C 18 heterocycles containing at least one heteroatom O, S, N, P, alkanes containing at least one halogen atom, and aromatic hydrocarbons containing at least one halogen atom; The ionic liquid is butyltrimethylammonium bis(trifluoromethanesulfonyl)imide, tributylmethyldibutylammonium phosphate, tributylmethylammonium chloride, tributylmethylmethylammonium carbonate, triethylmethyldibutylammonium phosphate, tetraethylammonium trifluoromethanesulfonate, trioctylmethylammonium hydrogen sulfate, ethyldimethylpropylammonium bis(trifluoromethanesulfonyl)imide, diethylmethyl-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium heptadecafluorooctanesulfonate, tetrabutylammonium nitrite, tetrabutylammonium hydroxide, tetrabutylammonium methanesulfonate, tetrabutylammonium bis(trifluoromethanesulfonyl)imide, tetrabutylammonium succinimide, tetrahexylammonium hydrogen sulfate, tetrahexylammonium iodide, tetraheptylammonium chloride, tetraheptylammonium bromide, tetra-n-butylammonium triiodide, tetrahexylammonium tetrafluoroborate , dodecyl ammonium tetrachloride, dodecyl ammonium tetrabromide, tetramethyl ammonium hydroxide, tetradecyl ammonium bromide, tetraoctylammonium chloride, methyl tributyl ammonium methyl sulfate, methyl tri(octadecyl) ammonium bromide, methyl trioctyl ammonium thiosalicylate, methyl-trioctylammonium bis(trifluoromethylsulfonyl)imide, 2-hydroxyethyl-trimethylammonium L-(+)-lactate, 2-hydroxy-N,N-di(2-hydroxyethyl)-N-methylethammonium methyl sulfate, benzyldimethyltetradecyl ammonium chloride, tetrabutylammonium benzoate, tetrabutylammonium thiophenol, choline acetate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-Butyl-4-methylpyridinium iodide, 1-ethylpyridinium tetrafluoroborate, 1-(3-cyanopropyl)pyridinium chloride, 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 4-(3-butyl-1-imidazole)-1-butane sulfonate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium dicyanamide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methyl 1-Butyl-3-methylimidazolium chloride, 1-Butyl-3-methylimidazolium bromide, 1-Butyl-3-methylimidazolium methanesulfonate, 1-Butyl-3-methylimidazolium nitrate, 1-Butyl-3-methylimidazolium hydrogen sulfate, 1-Butyl-3-methylimidazolium methyl sulfate, 1-Butyl-3-methylimidazolium octyl sulfate, 1-Butyl-3-methylimidazolium iodide, 1-Butyl-3-methylimidazolium hydrogen carbonate, 1-Butyl-3-methylimidazolium dibutyl phosphate, 1-Butyl-3-methylimidazolium trifluoromethanesulfonate, 1-Butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-methylimidazolium tetrachloroaluminate, 1-Butyl-3-methylimidazolium toluenesulfonate, 1-Butyl-3-methylimidazolium thiocyanate, 1,2,3-Trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolium ethylsulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium L-(+)-lactate, 1-ethyl-3-methylimidazolium dibutyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1- Ethyl-3-methylimidazolinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-3-methylimidazolium 1,1,2,2-tetrafluoroethylsulfonate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium nitrate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium p-toluenesulfonyl salt, 1-ethyl-3- Methyl imidazolium bromide, 1-ethyl-3-methylimidazolium iodide, 1,3-diethoxyimidazolium hexafluorophosphate, 1,3-diethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,2-dimethyl-3-propylimidazolium tris(trifluoromethylsulfonyl)methylate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethylimidazolium dimethylphosphine, 1,3-dimethylimidazolium methanesulfonate, 1,3-dimethylimidazolium methylsulfate, 1,3-dimethoxyimidazolium hexafluorophosphate, 1,3-dimethoxyimidazolium bis(trifluoromethylsulfonyl)imide, 1,3-dimethoxy-2-methylimidazolium hexafluorophosphate, 1,3-dimethoxy-2-methylimidazolium bis(trifluoromethylsulfonyl)imide imide, 1,3-dihydroxy-2-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1,3-dihydroxyimidazolium bis(trifluoromethanesulfonyl)imide, 1-dodecyl-3-methylimidazolium iodide, 1,3-bis(3-cyanopropyl)imidazolium chloride, 1,3-bis(cyanomethyl)imidazolium bis(trifluoromethanesulfonyl)imide, 1,3-bis(cyanomethyl)imidazolium chloride, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium chloride, 1-ethyl-2,3-Dimethylimidazolium, 1-ethyl-3-methylimidazolium chloride, 1-benzyl-3-methylimidazolium chloride, 1-(3-cyanopropyl)-3-imidazolium dicyanamide, 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, 1-(3-cyanopropyl)-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium dicyanamide, 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-methyl-3-propylimidazolium methyl carbonate, 1-methyl-3-propylimidazolium iodide, 1-methyl-3-vinylimidazole methyl carbonate, 1-methylimidazolium hydrogen sulfate, 1- Methylimidazolium chloride, 1-methyl-3-octylimidazolium trifluoromethanesulfonate, 1-methyl-3-octylimidazolium tetrafluoroborate, 1-methyl-3-octylimidazolium chloride, 1-decyl-3-methylimidazolium tetrafluoroborate, decylmethylimidazolium chloride, 1-hexyl-3-methylimidazolium iodide, 1-(2-hydroxyethyl)-3-methylimidazolium dicyanamide, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl- 3-Methylimidazolium hydrogen sulfate, 1-butyl-3-methylimidazolium methyl sulfate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium thiocyanate, 1,2,3-trimethylimidazolium methanesulfonic acid, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3-dimethylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium diethyl phosphate, 1-ethyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium tetrachloroaluminate, 1-ethyl-3-methylimidazolium methylsulfonate, 1-ethyl-3-methylimidazolium thiocyanate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium chloride, 1-methylimidazolium hydrogen sulfate, 1-methylimidazolium chloride, tributylmethylphosphine dibutyl phosphate, tributylmethylphosphine methylsulfate, triethylmethylphosphine dibutyl phosphate, trihexyltetradecylphosphine bromide, trihexyltetradecylphosphine chloride, trihexyltetradecylphosphine decanoate, trihexyl (tetradecyl) phosphine dicyanamide, trihexyltetradecylphosphine bis (trifluoromethylsulfonyl) amide, trihexyltetradecylphosphine bis (2,4,4-trimethylpentyl) hypophosphite, 3-(triphenylphosphino)propane-1-toluenesulfonyl, 3-(triphenylphosphino)propane-1-sulfonate, tetrabutylphosphine tetrafluoroborate, tetrabutylphosphine p-toluenesulfonate, tetrabutylphosphine methanesulfonate, 1-butyl-1-methylpyrrolidine trifluoromethanesulfonate, 1-butyl-1-methylpyrrolidine dinitrile amine salt, 1-butyl-1-methylpyrrolidine hexafluorophosphate, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine bis(trifluoromethanesulfonyl)imide, 1-butyl-1-methylpyrrolidine tetrafluoroborate, 1-butyl-1-methylpyrrolidine chloride, 1-butyl-1-methylpyrrolidine bromide, 1- any one of butyl-1-methylpyrrolidine iodide, 1-butyl-1-methylpyrrolidine methyl carbonate, 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-1-methylpyrrolidinium tetrafluoroborate, 1-methyl-1-ethylpyrrolidinium hexafluorophosphate, 1-methyl-1-ethylpyrrolidine bromide, triethylsulfonium bis(trifluoromethylsulfonyl)imide, cyclopropyldiphenylsulfonium tetrafluoroborate, 1-butyl-1-methylpiperidinium tetrafluoroborate, 1-butyl-1-methylpiperidinium hexafluorophosphate, 1-butyl-1-methylpiperidinium bis(trifluoromethylsulfonyl)imide, 4-ethyl-4-methylmorpholine methyl carbonate, and C 4-C 60 ionic liquids containing at least one S, N, or P heteroatom; The high molecular polymer is any combination of polystyrene, polypropylene, polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, polyisopropyl acrylate, polybutyl acrylate, polyisobutyl acrylate, polytert-butyl acrylate, polypentyl acrylate, polyisopentyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polypentyl methacrylate, polyisopentyl methacrylate, polyhexyl methacrylate, polyethylene glycol, polyvinyl alcohol, polyurethane, polyethylene, polycarbonate, polyamide, polytetrafluoroethylene, polyethylene terephthalate, polybutylene terephthalate, polyvinyl acetate, polysilicone, polyacrylonitrile, polychlorotrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, and polydimethylsilicate.

Images