CN114296283A - Electrochromic device and preparation method thereof - Google Patents
Electrochromic device and preparation method thereof Download PDFInfo
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- CN114296283A CN114296283A CN202111533903.2A CN202111533903A CN114296283A CN 114296283 A CN114296283 A CN 114296283A CN 202111533903 A CN202111533903 A CN 202111533903A CN 114296283 A CN114296283 A CN 114296283A
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Abstract
The invention discloses an electrochromic device and a preparation method thereof. The device includes: the organic electrochromic device comprises an anode transparent conductive substrate, an organic electrochromic layer positioned on the anode transparent conductive substrate, and a cathode transparent conductive substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the cathode transparent conductive substrate, and local high-concentration electrolyte is filled in the cavity; the cathode transparent conductive substrate is connected with the surface of the anode transparent conductive substrate uncovered by the organic electrochromic layer through a sealant; the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1: 0.1-1: 20, and the molar ratio of the conductive salt to the diluent is 1: 0.1-1: 40. The local high-concentration electrolyte constructed by the invention is used in an organic electrochromic device, and the broadening of a voltage window, the increase of optical contrast and good optical and electrochemical stability are realized.
Description
Technical Field
The invention relates to the technical field of electrochromic devices, in particular to an electrochromic device and a preparation method thereof.
Background
Electrochromic refers to the phenomenon in which an electroactive material undergoes a visually reversible color change under an external voltage,exhibit reversible changes in optical transmittance, reflectance, absorbance, and the like. Macroscopically, materials with electrochromic phenomena undergo a reversible coloration/discoloration state change. In a broad sense, electrochromic materials include inorganic electrochromic materials and organic electrochromic materials, the former mainly including commercialized WO3And the like metal oxides; the latter comprises conductive high molecular polymer, viologen micromolecule and derivatives, ester micromolecule and derivatives and the like. The organic electrochromic material has the advantages of adjustable color, high response speed, strong controllability and the like, but has the defects of poor stability, narrow potential window and the like in practical application, and greatly limits the commercial application of the organic electrochromic material.
The simple electrochromic device is composed of a double-layer conductive substrate, an electrochromic layer and an electrolyte layer. The electrolyte layer functions to conduct ions and block electron transport. Currently, electrolytes are classified by type into liquid electrolytes, gel electrolytes, and solid electrolytes. The commercialized devices mostly adopt low-concentration liquid electrolytes, and although the device adopting inorganic materials as electrochromic layers shows good stability, the electrolytes are difficult to be applied to organic electrochromic devices due to the defects of narrow potential window, side reaction of electrolyte and organic materials and the like. Therefore, it is urgent to find an electrolyte having high conductivity, wide voltage window, good chemical stability, and good compatibility with organic electrochromic materials.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an electrochromic device and a preparation method thereof, and aims to solve the problem that the existing electrolyte is incompatible with an organic electrochromic material.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, there is provided an electrochromic device, as shown in fig. 1, comprising: the solar cell comprises an anode transparent conductive substrate 1, an organic electrochromic layer 2 positioned on the anode transparent conductive substrate 1, and a cathode transparent conductive substrate 4 positioned above the organic electrochromic layer 2, wherein a cavity 3 is formed between the organic electrochromic layer 2 and the cathode transparent conductive substrate 4, and local high-concentration electrolyte is filled in the cavity 3; the cathode transparent conductive substrate 4 is connected with the surface of the anode transparent conductive substrate 1 which is not covered by the organic electrochromic layer 2 through a sealant 5;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1: 0.1-1: 20, and the molar ratio of the conductive salt to the diluent is 1: 0.1-1: 40.
The use of high electrolyte concentrations is a promising approach to reduce electrolyte decomposition by strong salt-solvation coordination. Although the use of nearly saturated lithium salt solutions of commercial solvents such as ethers, DMSO and the like in high concentration electrolytes can improve the stability and reversibility of the battery, its high viscosity, high cost and low oxygen solubility are very disadvantageous. To solve these problems in high concentration electrolytes, the present application contemplates localized high concentration electrolytes using a single Li+A non-coordinating co-solvent (typically polyfluoroether) is used to dilute the ultra-concentrated electrolyte so that the overall salt concentration in the electrolyte stays around the conventional 1.0M rather than in the ultra-concentrated state. The essence of this strategy is to separate the roles of the bulk of the electrolyte and the interface and to assign these roles to different stages on a microscopic scale.
The invention adopts local high-concentration electrolyte (belonging to organic system electrolyte) to replace the traditional organic electrolyte, effectively avoids the side reaction between the traditional organic electrolyte and the organic electrochromic material, overcomes the defects of poor electrochemical stability, narrow working window, larger flammability and the like of the common organic electrolyte under the traditional low concentration, can also effectively reduce the high cost caused by the concentrated salt in the high-concentration electrolyte, and effectively improves the optical contrast, the photoresponse rate, the electrochemical stability and the cycle life of the organic electrochromic device. The local high-concentration electrolyte has wide application prospect in the fields of electrochromic display, energy storage devices and the like.
Preferably, the molar ratio of the conductive salt to the solvent is 1: 0.5-1: 2, and the molar ratio of the conductive salt to the diluent is 1: 0.5-1: 2.
Preferably, the conductive salt is an alkali metalOne or two of salts, ammonium salts, and the like. By way of example, the conductive salt is lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium tetrafluoroborate (LiBF)4) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium trifluoroacetate (CF)3COOLi), lithium bistrifluoromethane succinimide (TFSILi), lithium Trifluoromethanesulfonate (TFSLi), sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) Sodium hexafluoroarsenate (NaAsF)6) Sodium tetrafluoroborate (NaBF)4) Sodium trifluoromethanesulfonate (NaCF)3SO3) Sodium trifluoroacetate (CF)3COONa), sodium bistrifluoromethane xanthimide (TFSINa), sodium trifluoromethanesulfonate (TFSNa), potassium hexafluorophosphate (KPF)6) Potassium perchlorate (KClO)4) Potassium hexafluoroarsenate (KAsF)6) Potassium tetrafluoroborate (KBF)4) Potassium trifluoromethanesulfonate (KCF)3SO3) Potassium trifluoroacetate (CF)3COOK), potassium bistrifluoromethane succinimide (TFSIK), potassium Trifluoromethanesulfonate (TFSK), ammonium hexafluorophosphate (NH)4PF6) Ammonium perchlorate (NH)4ClO4) Ammonium hexafluoroarsenate (NH)4AsF6) Ammonium tetrafluoroborate (NH)4BF4) Ammonium triflate (NH)4CF3SO3) Ammonium trifluoroacetate (CF)3COONH4) Bis (trifluoromethanesulfonimide) ammonium (TFSINH)4) Ammonium Triflate (TFSNH)4) And the like. It should be noted that, not limited to the above-mentioned conductive salts, conductive salts commonly used in electrochromic devices are applicable to the present invention.
Preferably, the solvent is an ether organic solvent. Examples of the ether organic solvent include one or more of ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, and diethylene glycol dimethyl ether (DG), propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, and diethylene glycol butyl ether acetate. It should be noted that the above listed solvents are only representative solvents, and are not limited to the above mentioned solvents, and common ether organic solvents are applicable to the present invention.
Preferably, the diluent is a fluoroether solvent.
By way of example, the fluoroether-based solvent is one or more of the structures shown below:
it should be noted that the above-mentioned fluoroether-based solvents are merely representative solvents, and are not limited to the above-mentioned fluoroether-based solvents, and commercially available fluoroether-based solvents are suitable for the present invention.
In the invention, the organic electrochromic layer is made of an organic polymer electrochromic material. Preferably, the material of the organic electrochromic layer is one or more of various electrochromic materials such as Poly (3-hexylthiophene-2,5-diyl) (P3HT), polyaniline electrochromic materials, polypyrrole electrochromic materials, polythiophene electrochromic materials, polybenzazole electrochromic materials, polyfuran electrochromic materials, polycarbazole and derivatives thereof electrochromic materials, D-A-D type polymers, D-A type polymers and copolymers thereof electrochromic materials.
Preferably, the material of the organic electrochromic layer is a small molecule electrochromic material (with a molecular weight within 1000), such as one or more of various small molecule electrochromic materials, for example, an ester electrochromic material, a viologen electrochromic material, and the like.
Further preferably, the ester electrochromic material is one or more of the following structures:
further preferably, the viologen small molecule organic electrochromic material is one or more of the following structures:
further preferably, the other small molecule organic electrochromic material is one or more of the following structures:
further preferably, the polyaniline electrochromic material is one or more of the following structures:
further preferably, the polypyrrole electrochromic material is one or more of the following structures:
in a second aspect of the present invention, there is provided a method for preparing an electrochromic device as described above, wherein the method comprises the steps of:
s10, preparing an organic electrochromic layer on the anode transparent conductive substrate;
s11, coating sealant on the peripheral frame of the anode transparent conductive substrate covered by the organic electrochromic layer, and reserving an electrolyte injection port;
s12, covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant, and forming a cavity between the organic electrochromic layer and the cathode transparent conductive substrate;
s13, injecting partial high-concentration electrolyte into the cavity through the electrolyte injection port, and finally sealing the electrolyte injection port by sealant; wherein the localized high concentration electrolyte comprises a solvent, a conductive salt, and a diluent.
Preferably, step S10 specifically includes:
dissolving an organic electrochromic material in common organic solvents such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene and the like to obtain an organic electrochromic material solution;
and uniformly covering the organic electrochromic material solution on an anode transparent conductive substrate by adopting a spraying method to obtain the organic electrochromic layer.
In step S13, preferably, the method for preparing the local high-concentration electrolyte solution includes the steps of:
injecting a solvent into the conductive salt, and uniformly stirring to obtain a conductive salt solution;
and adding a diluent into the conductive salt solution, and uniformly stirring to obtain the local high-concentration electrolyte.
Preferably, the stirring time is 0.5-10 h.
In a third aspect of the present invention, there is provided a method for preparing an electrochromic device as described above, wherein the method comprises the steps of:
s20, mixing the small-molecule organic electrochromic material with local high-concentration electrolyte to obtain a mixed solution; wherein the localized high concentration electrolyte comprises a solvent, a conductive salt, and a diluent;
s21, coating sealant or bonding double-sided adhesive tape on the peripheral frame of the anode transparent conductive substrate, and reserving an electrolyte injection port;
s22, covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant or bonded with the double-sided adhesive, and forming a cavity between the anode transparent conductive substrate and the cathode transparent conductive substrate;
and S23, injecting the mixed solution into the cavity through the electrolyte injection port, and finally sealing the electrolyte injection port by adopting a sealant.
In step S20, preferably, in the mixed solution, the total concentration of the small molecule organic electrochromic material and the ionic salt of the local high-concentration electrolyte is 1 mol/L.
The novel local high-concentration electrolyte is constructed based on the traditional organic electrolyte and is used in the organic electrochromic device, so that the broadening of a voltage window, the increase of optical contrast and good optical and electrochemical stability are realized, the instability of an organic electrochromic material is effectively overcome, and the marketization application of the organic electrochromic device is promoted.
Drawings
Fig. 1 is a schematic structural diagram of an electrochromic device provided in the present invention.
FIG. 2 shows an example 1 of the present invention containing LiTFSI (TGE)1.75(BTE)3.5P3HT electrochromic device CV curve for a locally high concentration of electrolyte.
FIG. 3 shows an example 1 of the present invention containing LiTFSI (TGE)1.75(BTE)3.5P3HT electrochromic device with local high concentration of electrolyte has ultraviolet and visible absorption spectrum of the device under different potentials.
FIG. 4 shows an example 1 of the present invention containing LiTFSI (TGE)1.75(BTE)3.5Optical contrast of P3HT electrochromic device with locally high concentration of electrolyte.
FIG. 5 shows the composition of example 5 of the present invention containing LiTFS (DME)1(TTE)2DTP electrochromic device CV curve for locally high electrolyte concentration.
FIG. 6 shows the composition of example 5 containing LiTFS (DME)1(TTE)2And the DTP electrochromic device with the local high-concentration electrolyte has an ultraviolet visible absorption spectrum under different potentials.
FIG. 7 shows an example 5 of the present invention containing LiTFS (DME)1(TTE)2Optical contrast of DTP electrochromic devices with locally high concentration of electrolyte.
FIG. 8 shows LiTFSI (TGE) in comparative example 1 of the present invention4(BTE)4DTP electrochromic devices of electrolyte the optical contrast of the electrochromic devices.
Detailed Description
The present invention provides an electrochromic device and a method for manufacturing the same, and the present invention is further described in detail below in order to make the objects, technical solutions, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
1.1, dissolving TFSILi in tetraethylene glycol diethyl ether (TGE) solvent at a molar ratio of 1:1.75, stirring for 2h at room temperature to obtain a uniform conductive salt solution, then adding a bis (2,2, 2-trifluoroethyl) ether (BTE) diluent into the conductive salt solution, and stirring uniformly again to obtain transparent LiTFSI (TGE)1.75(BTE)3.5A local high concentration electrolyte;
1.2, preparing a P3HT organic electrochromic layer on an anode transparent conductive substrate;
1.3, coating sealant on the peripheral frame of the anode transparent conductive substrate covered by the P3HT organic electrochromic layer, and reserving an electrolyte injection port;
1.4, covering a cathode transparent conductive substrate on the anode transparent conductive substrate obtained in the step 1.3, and forming a cavity between the P3HT organic electrochromic layer and the cathode transparent conductive substrate;
1.5 injecting LiTFSI (TGE) into the cavity through the electrolyte injection port1.75(BTE)3.5And finally, sealing the electrolyte injection opening by adopting sealant.
In this example, the composition contains LiTFSI (TGE)1.75(BTE)3.5The P3HT electrochromic device with a locally high concentration of electrolyte undergoes a color change under an applied voltage, the device is red at 0V, and when a positive voltage is applied to reach 3.0V, the device changes to a transparent blue color. FIG. 2 shows a schematic diagram of a circuit including LiTFSI (TGE)1.75(BTE)3.5CV curve of P3HT electrochromic device with locally high concentration of electrolyte. FIG. 3 shows the UV-visible absorption spectrum of the device at different potentials, where it can be seen that at 3.0V, the absorption peak at 520nm disappears and the absorption intensity increases in the near infrared wavelength range (> 800 nm). FIG. 4 shows a schematic diagram of a structure containing LiTFSI (TGE)1.75(BTE)3.5The optical contrast of the P3HT electrochromic device with a locally high concentration of electrolyte is 94.6% at 610nm, 86.8% at 1500nm, and the photoresponse rate is 4.5s/4s (coloration/discoloration), as can be seen from the graph.
Example 2
2.1 preparation of LiBF4Dissolving the mixture in diethylene glycol dimethyl ether (DGE) solvent in a molar ratio of 1:0.8, stirring the mixture for 2 hours at room temperature to obtain a uniform conductive salt solution, then adding 1,1,2,3,3, 3-hexafluoropropyl ethyl ether (HFE) diluent into the conductive salt solution, and stirring the mixture uniformly again to obtain transparent LiBF4(DGE)0.8(HFE)1.6A local high concentration electrolyte;
2.2, preparing a P3HT organic electrochromic layer on an anode transparent conductive substrate;
2.3, coating sealant on the peripheral frame of the anode transparent conductive substrate covered by the P3HT organic electrochromic layer, and reserving an electrolyte injection port;
2.4, covering a cathode transparent conductive substrate on the anode transparent conductive substrate obtained in the step 2.3, and forming a cavity between the P3HT organic electrochromic layer and the cathode transparent conductive substrate;
2.5 injecting LiBF into the cavity through the electrolyte injection port4(DGE)0.8(HFE)1.6And finally, sealing the electrolyte injection opening by adopting sealant.
The performance of the electrochromic device obtained in this example was substantially the same as that of example 1, and when a voltage of 3.0V was applied, the absorption peak at 610nm disappeared, and the absorption intensity in the near-infrared wavelength range (> 800nm) increased. The optical contrast at 610nm was-94%, the optical contrast at 1500nm was-85%, and the photoresponse rate was 4.7s/4s (coloration/discoloration).
Example 3
The preparation method of the electrochromic device of this example is the same as that of example 1, except that: the solvent is ethylene glycol monobutyl ether (BE), the diluent is 1H,1H, 5H- octafluoropentyl 1,1,2, 2-tetrafluoro ethyl ether (OTE), and the local electrolyte is replaced by LiTFS (BE)0.8(OTE)4。
The performance of the electrochromic device obtained in this example was substantially the same as that of example 1, and when a voltage of 3.0V was applied, the absorption peak at 520nm disappeared, and the absorption intensity in the near-infrared wavelength range (> 800nm) increased. The optical contrast at 610nm was-43%, the optical contrast at 1500nm was-22%, and the photoresponse rate slowed to 12.6s/12.4s (coloration/discoloration).
Example 4
The preparation method of the electrochromic device of this example is the same as that of example 1, except that: the solvent is ethylene glycol Monomethyl Ether (ME), the diluent is 1,1,2, 2- tetrafluoroethyl 2,2,3, 3-tetrafluoropropyl ether (TTE), and the local electrolyte is replaced by LiTFSI (ME)0.8(TTE)4。
The performance of the electrochromic device obtained in the example is basically the same as that of the electrochromic device obtained in the example 1, when a voltage of 3.0V is applied, the device is completely changed into blue, the absorption peak of the device in a visible light region at 520nm disappears, and the absorption intensity in a near infrared wavelength range (more than 800nm) is increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the photoresponse rate slowed to 12.6s/12.4s (coloration/discoloration).
Example 5
5.1, dissolving TFSLi in a glycol dimethyl ether (DME) solvent according to a molar ratio of 1:1, stirring for 2 hours at room temperature to obtain a uniform conductive salt solution, then adding a 1,1,2, 2- tetrafluoroethyl 2,2,3, 3-tetrafluoropropyl ether (TTE) diluent into the conductive salt solution, and stirring uniformly again to obtain transparent LiTFS (DME)1(TTE)2A local high concentration electrolyte;
5.2 Dimethyl Terephthalate (DTP) dissolved at 10mM in LiTFS (DME) in step 5.11(TTE)2Obtaining a mixed solution in local high-concentration electrolyte;
5.3, tightly adhering the conductive side of the double-layer conductive ITO glass by using a double-sided adhesive tape, reserving an electrolyte injection port, and forming a cavity between the double-layer conductive ITO glass;
and 5.4, injecting the mixed solution prepared in the step 5.2 into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting a sealant.
In this example, the catalyst contains LiTFS (DME)1(TTE)2The DTP electrochromic device with local high-concentration electrolyte is subjected to color change under the external voltage, the device is transparent and colorless at 0V, and the device is changed into opaque red when the applied voltage reaches-4.0V. FIG. 5 shows a reaction system containing LiTFS (DME)1(TTE)2CV curve of DTP electrochromic device with locally high concentration of electrolyte. FIG. 6 shows the UV-visible absorption spectrum of the device at different potentials, where it can be seen that the intensity of the absorption peak at 544nm is at a maximum at-4V. FIG. 7 shows a reaction system containing LiTFS (DME)1(TTE)2The optical contrast of the DTP electrochromic device with a locally high concentration of electrolyte is 49.8% at 544nm, and the photoresponse rate is 9s/9s (coloring/discoloring) as can be seen from the figure.
Example 6
This implementationExample electrochromic device was prepared as in example 5, except that: local electrolyte replacement to LiBF4(DME)1.75(TFE)3。
The performance of the electrochromic device obtained in the embodiment is basically the same as that of the electrochromic device obtained in the embodiment 5, when a voltage of-4.0V is applied, the device is completely red, the intensity of an absorption peak at 544nm reaches the maximum, and the absorption intensity in a near infrared wavelength range (more than 800nm) is increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the photoresponse rate slowed to 9.4s/9s (coloration/discoloration).
Example 7
The preparation method of the electrochromic device of this example is the same as that of example 5, except that: local electrolyte is changed into LiTFS (ME)1.75(BTE)3.5。
The performance of the electrochromic device obtained in the embodiment is basically the same as that of the electrochromic device obtained in the embodiment 5, when a voltage of-4.0V is applied, the device is completely red, the intensity of an absorption peak at 544nm reaches the maximum, and the absorption intensity in a near infrared wavelength range (more than 800nm) is increased. The optical contrast at 610nm was-68%, the optical contrast at 1500nm was-86%, and the photoresponse rate slowed to 8s/7.8s (coloration/discoloration).
Comparative example 1
The preparation method of the electrochromic device of this example is the same as that of example 1, except that: electrolyte was changed to LiTFSI (TGE)4(BTE)4As shown in fig. 8, the optical contrast of the DTP electrochromic device obtained in this example is only 8% at 520nm, and is decreasing.
Comparative example 2
The preparation method of the electrochromic device of this example is the same as that of example 5, except that: using an electrolyte of LiTFSI (ME)1.5(BTE)1The electrolyte is in a semi-solid state at room temperature, lithium salt is not completely dissolved, the light transmittance of the device is seriously influenced, and the device cannot normally work.
Comparative example 3
The preparation method of the electrochromic device of this example is the same as that of example 5, except that: using electrolyte LiTFSI (TGE)3(BTE)5DTP is rapid during electrochromic cyclingThe deactivation, the optical contrast rapidly decreases and the device no longer suffers discoloration.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. An electrochromic device, comprising: the organic electrochromic device comprises an anode transparent conductive substrate, an organic electrochromic layer positioned on the anode transparent conductive substrate, and a cathode transparent conductive substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the cathode transparent conductive substrate, and local high-concentration electrolyte is filled in the cavity; the cathode transparent conductive substrate is connected with the surface of the anode transparent conductive substrate uncovered by the organic electrochromic layer through a sealant;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1: 0.1-1: 20, and the molar ratio of the conductive salt to the diluent is 1: 0.1-1: 40.
2. The electrochromic device according to claim 1, wherein the conductive salt is one or both of an alkali metal salt and an ammonium salt.
3. The electrochromic device according to claim 1, the conductive salt is one or more of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium trifluoroacetate, lithium bistrifluoromethane xanthimide, lithium trifluoromethanesulfonate, sodium hexafluorophosphate, sodium perchlorate, sodium hexafluoroarsenate, sodium tetrafluoroborate, sodium trifluoromethanesulfonate, sodium trifluoroacetate, sodium bistrifluoromethane xanthimide, sodium trifluoromethanesulfonate, potassium hexafluorophosphate, potassium perchlorate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium trifluoromethanesulfonate, potassium trifluoroacetate, potassium bistrifluoromethane xanthimide, potassium trifluoromethanesulfonate, ammonium hexafluorophosphate, ammonium hexafluoroarsenate, ammonium tetrafluoroborate, ammonium trifluoromethanesulfonate, ammonium trifluoroacetate, ammonium bistrifluoromethane xanthimide and ammonium trifluoromethanesulfonate.
4. The electrochromic device according to claim 1, wherein said solvent is an ether-based organic solvent which is one or more of ethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, tetrahydrofuran, 2-methyl tetrahydrofuran, 1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol butyl ether, ethylene glycol phenyl ether, diethylene glycol butyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, diethylene glycol butyl ether acetate.
5. The electrochromic device according to claim 1, wherein said diluent is a fluoroether-based solvent.
6. The electrochromic device according to claim 1, wherein the molar ratio of the conductive salt to the solvent is 1:0.5 to 1:2, and the molar ratio of the conductive salt to the diluent is 1:0.5 to 1: 2.
7. The electrochromic device according to claim 1, wherein the material of the organic electrochromic layer is one or more of P3HT, polyaniline electrochromic materials, polypyrrole electrochromic materials, polythiophene electrochromic materials, polybenzazole electrochromic materials, polyfuran electrochromic materials, polycarbazole and its derivatives electrochromic materials, D-a-D type polymers, D-a type polymers and their copolymers electrochromic materials, ester electrochromic materials, and viologen electrochromic materials.
8. A method for preparing an electrochromic device according to any one of claims 1 to 7, characterized in that it comprises the steps of:
preparing an organic electrochromic layer on an anode transparent conductive substrate;
coating sealant on the peripheral frame of the anode transparent conductive substrate covered by the organic electrochromic layer, and reserving an electrolyte injection port;
covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant, wherein a cavity is formed between the anode transparent conductive substrate and the cathode transparent conductive substrate;
injecting partial high-concentration electrolyte into the cavity through the electrolyte injection port, and finally sealing the electrolyte injection port by adopting sealant;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1: 0.1-1: 20, and the molar ratio of the conductive salt to the diluent is 1: 0.1-1: 40.
9. A method for preparing an electrochromic device according to any one of claims 1 to 7, characterized in that it comprises the steps of:
mixing a small-molecule organic electrochromic material with local high-concentration electrolyte to obtain a mixed solution;
coating sealant or bonding double-sided adhesive on the peripheral frame of the anode transparent conductive substrate, and reserving an electrolyte injection port;
covering a cathode transparent conductive substrate on the anode transparent conductive substrate coated with the sealant or bonded with the double-sided adhesive, wherein a cavity is formed between the anode transparent conductive substrate and the cathode transparent conductive substrate;
injecting the mixed solution into the cavity through the electrolyte injection opening, and finally sealing the electrolyte injection opening by adopting a sealant;
the local high-concentration electrolyte comprises a solvent, a conductive salt and a diluent, wherein the molar ratio of the conductive salt to the solvent is 1: 0.1-1: 20, and the molar ratio of the conductive salt to the diluent is 1: 0.1-1: 40.
10. The method for preparing an electrochromic device according to claim 8 or 9, wherein the method for preparing the locally high-concentration electrolyte comprises the steps of:
injecting a solvent into the conductive salt, and stirring to obtain a conductive salt solution;
and adding a diluent into the conductive salt solution, and stirring to obtain the local high-concentration electrolyte.
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