CN110501852B - Electrochromic device based on high-concentration aqueous electrolyte and preparation method thereof - Google Patents
Electrochromic device based on high-concentration aqueous electrolyte and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an electrochromic device based on high-concentration water system electrolyte and a preparation method thereof, wherein the device comprises: the electrode comprises a first electrode substrate, an organic electrochromic layer positioned on the first electrode substrate, and a second electrode substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the second electrode substrate, and high-concentration aqueous electrolyte is filled in the cavity and is aqueous solution of fluorine-containing lithium salt with the concentration of 13-21 mol/L; the second electrode substrate is connected with the surface of the first electrode substrate uncovered by the organic electrochromic layer through a sealant. The invention replaces the traditional low-concentration water system electrolyte with the high-concentration water system electrolyte to construct the electrochromic device, overcomes the defects of damage of the traditional low-concentration water system electrolyte to the organic electrochromic layer, easy volatilization of the organic solvent-based electrolyte, high toxicity and the like, and realizes higher contrast in a near infrared region under the condition of ensuring high contrast in a visible region.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to an electrochromic device based on high-concentration water system electrolyte and a preparation method thereof.
Background
Electrochromism refers to reversible optical property (such as transmittance, absorbance and the like) change of a material caused by redox reaction driven by an external electric field, and macroscopic expression is that the color of the material is reversibly changed between a colored state and a faded state or between two colored states along with the change of the external electric field. Materials with electrochromic property are called electrochromic materials and are divided into inorganic electrochromic materials and organic electrochromic materials according to different material structures, and currently, most studied inorganic electrochromic materials comprise tungsten trioxide, Prussian blue and the like; the organic electrochromic material comprises viologen organic micromolecules and conductive high molecular polymers such as polypyrrole, polythiophene, polyaniline and the like. The inorganic electrochromic material has the defects of narrow color change range, poor optical contrast, slow response speed and the like; the organic electrochromic material has the advantages of strong controllability of structure and color change range, rich color change, easiness in processing into devices and high response speed, but the organic electrochromic material has poor stability and high contrast only in a visible light region, so that the commercial application of the organic electrochromic material is limited.
The device made of electrochromic materials is called an electrochromic device, and the electrochromic device is generally composed of two conductive substrates, an electrochromic layer, an electrolyte and an ion storage layer, wherein the electrochromic layer, the electrolyte and the ion storage layer are positioned between the two conductive substrates, and the electrolyte is usually transparent and plays a role in blocking electron transmission. At present, liquid electrolyte, gel electrolyte or similar solid electrolyte is mostly adopted by electrochromic devices; as a liquid electrolyte, although an aqueous electrolyte is more environment-friendly and safer than an organic electrolyte in device commercial application, the organic electrochromic material is prepared by using a traditional low-concentration aqueous electrolyte (such as 0.05-0.1M LiClO)4LiCl, or CH3COOLi, etc.), and is easy to leak liquid to cause short lifetime of the device, so that it is urgent to find an electrolyte having high conductivity, good chemical stability, and no damage to the device. In addition, due to the limitation of the functions of the organic electrochromic material and the water-based electrolyte, the existing electrochromic device can be applied to the visible light region more, and the existing electrochromic device has great defects in the near infrared region. Although some organic electrochromic materials can show the change of transmittance in a near infrared region under the control of voltage, the transmittance difference of an electrochromic device is small due to the limitation of an electrolyte.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide an electrochromic device based on a high-concentration aqueous electrolyte and a method for manufacturing the same, which aims to solve the problems of short lifetime and poor color change performance in the near-infrared region of the conventional organic electrochromic device.
The technical scheme of the invention is as follows:
an electrochromic device based on a high-concentration aqueous electrolyte, comprising: the electrode comprises a first electrode substrate, an organic electrochromic layer positioned on the first electrode substrate, and a second electrode substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the second electrode substrate, and high-concentration aqueous electrolyte is filled in the cavity and is aqueous solution of fluorine-containing lithium salt with the concentration of 13-21 mol/L;
the second electrode substrate is connected with the surface of the first electrode substrate uncovered by the organic electrochromic layer through a sealant.
The electrochromic device based on the high-concentration aqueous electrolyte is characterized in that the fluorine-containing lithium salt is selected from one or more of lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate and lithium bistrifluorosulfonylimide.
The electrochromic device based on the high-concentration water-based electrolyte is characterized in that the material of the organic electrochromic layer is TQ1 or P3 HT.
The electrochromic device based on the high-concentration aqueous electrolyte is characterized in that the first electrode substrate and the second electrode substrate are independently selected from one of ITO glass, PET/ITO and PDMS/Ag nanowires.
A method for preparing an electrochromic device based on a high-concentration aqueous electrolyte as described above, comprising the steps of:
A. preparing an organic electrochromic layer on a first electrode substrate;
B. coating sealant on the surface of the first electrode substrate uncovered around the organic electrochromic layer, and reserving an injection port;
C. covering a second electrode substrate above the organic electrochromic layer and attaching the second electrode substrate to the sealant, wherein a cavity is formed between the second electrode substrate and the organic electrochromic layer;
D. a highly concentrated aqueous electrolyte is added to the cavity from the injection port, and the injection port is then sealed with a sealant.
The preparation method of the electrochromic device based on the high-concentration aqueous electrolyte is characterized in that in the step A, the method for preparing the organic electrochromic layer is selected from one of spray coating, electrochemical deposition and spin coating.
The preparation method of the electrochromic device based on the high-concentration aqueous electrolyte specifically comprises the following steps: dissolving the organic electrochromic layer material in an organic solvent, spraying the organic electrochromic layer material on the surface of the first electrode substrate, and drying; the organic solvent is chloroform or chlorobenzene.
The preparation method of the electrochromic device based on the high-concentration aqueous electrolyte comprises the following steps in step D: and mixing the deionized water with the fluorine-containing lithium salt to form the high-concentration aqueous electrolyte.
The preparation method of the electrochromic device based on the high-concentration aqueous electrolyte is characterized in that the mixing temperature is 25-60 ℃.
The preparation method of the electrochromic device based on the high-concentration aqueous electrolyte is characterized in that the mixing time is 2-6 h.
Has the advantages that: according to the invention, a high-concentration aqueous electrolyte (13-21 mol/L aqueous solution containing fluorine lithium salt) is used for replacing a traditional low-concentration aqueous electrolyte for an electrochromic device based on the high-concentration aqueous electrolyte constructed by an organic electrochromic device, so that the defects of short service life, narrow working window, easy volatilization of organic solvent-based electrolyte, high toxicity and the like of the organic electroluminescent device caused by the damage of the traditional low-concentration aqueous electrolyte to an organic electrochromic layer are overcome, and the special high contrast in a near infrared region is realized under the condition of ensuring the high contrast in a visible light region; the electrochromic device based on the high-concentration water system electrolyte has the advantages of long service life, quick response and good memory, and has guiding significance for the application of the high-concentration water system electrolyte in the fields of electrochromic display, intelligent windows, military camouflage and the like.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of an electrochromic device based on a high-concentration aqueous electrolyte according to an embodiment of the present invention.
Fig. 2 is a CV curve measured at different scan rates of the electrochromic device based on the high-concentration aqueous electrolyte prepared in example 1 of the present invention.
Fig. 3 shows the uv-vis absorption spectra of the electrochromic device based on a high concentration aqueous electrolyte prepared in example 1 of the present invention measured at different voltages.
Fig. 4 is a graph showing transmittance changes at different wavelengths of the electrochromic device based on the high concentration aqueous electrolyte prepared in example 1 of the present invention.
Fig. 5 is a CV curve measured at the same scanning rate for an electrochromic device based on a high-concentration aqueous electrolyte prepared in example 4 of the present invention.
Fig. 6 shows uv-vis absorption spectra of electrochromic devices based on high concentration aqueous electrolytes prepared in example 4 of the present invention measured at different voltages.
Fig. 7 is a graph showing transmittance changes at different wavelengths of an electrochromic device based on a high concentration aqueous electrolyte prepared in example 4 of the present invention: 7a is a graph of the change in transmittance at 530 nm; FIG. 7b is a graph showing the change in transmittance at 1500 nm.
Fig. 8 is a graph showing the transmittance change at 1500nm of the electrochromic device manufactured in comparative example 1 of the present invention.
Fig. 9 is a graph showing the transmittance change at different wavelengths of the electrochromic device manufactured in comparative example 2 according to the present invention.
Detailed Description
The present invention provides an electrochromic device based on a high concentration aqueous electrolyte and a method for manufacturing the same, and the present invention will be described in further 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.
The embodiment of the invention provides an electrochromic device based on a high-concentration water system electrolyte, which comprises: the electrode comprises a first electrode substrate, an organic electrochromic layer positioned on the first electrode substrate, and a second electrode substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the second electrode substrate, and high-concentration aqueous electrolyte is filled in the cavity and is aqueous solution of fluorine-containing lithium salt with the concentration of 13-21 mol/L;
the second electrode substrate is connected with the surface of the first electrode substrate uncovered by the organic electrochromic layer through a sealant.
Specifically, the sectional structure of the electrochromic device based on the high concentration aqueous electrolyte of the present embodiment is shown in fig. 1, where 1 is a first electrode substrate; 2 is an organic electrochromic layer; 3 is a cavity, and the high-concentration water system electrolyte is positioned in the cavity 3; 4 is a second electrode substrate; and 5 is an area of the surface of the first electrode substrate, which is not covered by the organic electrochromic layer, namely the area where the sealant is located.
In the embodiment, a high-concentration aqueous electrolyte (13-21 mol/L aqueous solution of a fluorine-containing lithium salt) is used for replacing a traditional low-concentration aqueous electrolyte for constructing an electrochromic device based on the high-concentration aqueous electrolyte for an organic electrochromic device, so that the defects of short service life, narrow working window, easy volatilization of an organic solvent-based electrolyte, high toxicity and the like of the organic electroluminescent device caused by the damage of the traditional low-concentration aqueous electrolyte to an organic electrochromic layer are overcome, and the special high contrast in a near infrared region is realized under the condition of ensuring the high contrast in a visible light region; the electrochromic device based on the high-concentration water system electrolyte has the advantages of long service life, quick response and good memory, and has guiding significance for the application of the high-concentration water system electrolyte in the fields of electrochromic display, intelligent windows, military camouflage and the like. Specifically, the high-concentration aqueous electrolyte (13 to 21mol/L aqueous solution of fluorine-containing lithium salt) in the embodiment has a high ion diffusion rate and high ionic conductivity, so that the response of the electrochromic device is fast. In addition, in the high-concentration aqueous electrolyte (13-21 mol/L aqueous solution of fluorine-containing lithium salt) in the embodiment, fluorine ions are strong electron-withdrawing groups, and the existing form of water is not free water any longer, but is crystal water; in the electrolyte of more than or equal to 13M, 4 water is not around the lithium ion, but as the concentration is increased, the electrolyte anion (anion) participates in the lithium ion coordination to form Li (anion)x(H2O)4-xStructure; although the stability of the organic material in common water is poor and the structure is easy to damage, the stability of the organic material is not influenced by the crystal water, and the water in the electrolyte can be effectively avoidedDue to the influence of the organic material, the electrolyte exists in a gel-like state within a limited concentration range (13-21 mol/L), but when the concentration exceeds 21mol/L, electrolyte salt can be precipitated at normal temperature, so that the conductivity of electrolyte ions is reduced, and the responsiveness of an electrochromic device is influenced. The electrolyte is in a gel state, and is infinitely close to a quasi-solid state along with the higher concentration; so that there is a large amount of Li (anion) at the interface of the electrolyte and the electrochromic layerx(H2O)4-xWhen the ion extraction rate is extremely slow after the applied voltage is removed, the electrochromic device containing the high-concentration aqueous electrolyte according to this embodiment has good memory.
When the organic electrochromic layer material is an oxidative electrochromic material, the first electrode substrate is an anode substrate, and the second electrode substrate is a cathode substrate; when the organic electrochromic layer is made of a reduction color-changing material, the first electrode substrate is a cathode substrate, and the second electrode substrate is an anode substrate; the first electrode substrate and the second electrode substrate are both transparent electrode substrates.
In one embodiment, the fluorine-containing lithium salt may be selected from, but is not limited to, one or more of lithium bistrifluoromethanesulfonimide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluorosulfonimide. The high-concentration water-based electrolyte formed by dissolving the fluorine-containing lithium salt in water can enable electrolyte ions to show own electrochemical properties by limiting the free movement of water; the high-concentration aqueous electrolyte is highly environment-friendly.
In one embodiment, the organic electrochromic layer material may be, but is not limited to, TQ1 or P3 HT. Specifically, poly [ [2, 3-bis (3-octyloxyphenyl) -5, 8-quinoxalinediyl]-2, 5-thiophenediyl]（Poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl]TQ 1) is as follows
The structural formula of Poly (3-hexyl-thiophene-2,5-diyl) P3HT is
. In the electrochromic device containing the high-concentration water system electrolyte, the stored charges of the electrochromic layer are increased, the concentration is increased, and more anions are promoted to participate in the reaction; the absorption near the infrared is related to the band gap of the electrochromic material, when a positive voltage is applied to the working electrode, the electrochromic oxidation process is a doping process, and the polymer chain of the electrochromic polymer gradually realizes complete doping along with the increase of the number of anions participating in reaction; the number of dedoping ions increases correspondingly when a reverse voltage is applied.
In an embodiment, the first electrode substrate and the second electrode substrate are independently selected from one of ITO glass, PET/ITO, PDMS/Ag nanowires. Specifically, ITO is indium tin oxide; PET is a poly (terephthalic acid) plastic such as Polyethylene terephthalate (Polyethylene terephthalate); PDMS is polydimethylsiloxane (polydimethylsiloxane).
The embodiment of the invention also provides a preparation method of the electrochromic device based on the high-concentration aqueous electrolyte, which comprises the following steps:
A. preparing an organic electrochromic layer on a first electrode substrate;
B. coating a sealant on the surface of the first electrode substrate uncovered by the organic electrochromic layer, and reserving an injection port;
C. covering a second electrode substrate above the organic electrochromic layer and attaching the second electrode substrate to the sealant, wherein a cavity is formed between the second electrode substrate and the organic electrochromic layer;
D. a highly concentrated aqueous electrolyte is added to the cavity from the injection port, and the injection port is then sealed with a sealant.
The electrochromic device based on the high-concentration water system electrolyte has a simple preparation process, and is beneficial to realizing industrial production and application; the optical contrast, the optical memory and the color conversion rate of the electrochromic device in the near infrared region can be adjusted by controlling the concentration of the high-concentration water-based electrolyte.
In one embodiment, in step a, the method for preparing the organic electrochromic layer is selected from one of spray coating, electrochemical deposition, and spin coating. Wherein, the spraying specifically includes: dissolving the organic electrochromic layer material in an organic solvent, spraying the organic electrochromic layer material on the surface of the first electrode substrate, and drying; the organic solvent is chloroform or chlorobenzene.
In one embodiment, in step D, the method for preparing the high-concentration aqueous electrolyte comprises the steps of: and mixing the deionized water with the fluorine-containing lithium salt to form the high-concentration aqueous electrolyte. Wherein the mixing temperature is 25-60 ℃; the mixing time is 2-6 h.
The present invention will be described in detail below with reference to specific examples.
Example 1
(1) 1mL of water and 15mmol of lithium bis (trifluoromethanesulfonylimide) (TFSILi) are stirred at 40 ℃ for 4 hours and fully mixed, and the obtained high-concentration water system electrolyte is 15mol/L of aqueous solution of TFSILi;
(2) spraying a TQ1 solution on a first electrode substrate (an anode substrate, ITO glass), and drying to prepare an organic electrochromic layer;
(3) coating sealant on the surface of the first electrode substrate uncovered around the organic electrochromic layer, and reserving an injection port;
(4) covering a second electrode substrate (cathode substrate, ITO glass) above the organic electrochromic layer and attaching the second electrode substrate to the sealant, wherein a cavity is formed between the second electrode substrate and the organic electrochromic layer;
(5) and injecting the prepared aqueous solution of 15mol/L TFSILi into the cavity, and then sealing the injection hole by using a sealant to obtain the electrochromic device based on the high-concentration aqueous electrolyte.
The CV curves of the electrochromic device based on the high-concentration aqueous electrolyte prepared in the example at different scanning speeds are shown in FIG. 2, which shows that the electrochromic device can maintain good oxidation-reduction stability at different scanning speeds, and the oxidation potential of the polymer TQ1 is about 1.0V. The ultraviolet and visible absorption spectra of the electrochromic device based on the high-concentration aqueous electrolyte prepared in the example measured under different voltages are shown in fig. 3, the maximum absorption wavelength of the visible film in a neutral state (applied voltage of-0.2V) is 610nm, the device is blue, the absorption at the wavelength is weakened along with the increase of the voltage, the maximum absorption at 1900nm is realized when the electrochromic layer is in a completely oxidized state (applied voltage of 2.0V), and the device is completely transparent; and at 1.6V, the absorption peak at 610nm is obviously reduced, and the absorption intensity in the near infrared wavelength range (more than 800 nm) is increased. The transmittance change at different wavelengths of the electrochromic device based on the high concentration aqueous electrolyte prepared in this example is shown in fig. 4, from which it can be seen that the optical contrast at 610nm is 43.02%, and the optical contrast at 1500nm is 22.48%.
Example 2
The electrochromic device was prepared as in example 1, except that: 1mL of water and 14mmol of lithium Trifluoromethanesulfonate (TFLi) are fully mixed at 25 ℃ for 2 hours under stirring, and the obtained high-concentration water-based electrolyte is 14mol/L of an aqueous solution of TFLi; the performance of the electrochromic device prepared based on the high-concentration aqueous electrolyte (14 mol/L aqueous solution of TFLi) is basically the same as that of the electrochromic device prepared in the embodiment 1, when the electrochromic device is in a neutral state of-0.2V-0V, the device is blue, after the voltage is applied for 1.6V, the device is changed from blue to transparent, the absorption peak at 610nm is reduced, and the absorption intensity in a near infrared wavelength range (more than 800 nm) is increased. The optical contrast at 610nm is-43%, and the optical contrast at 1500nm is-22%.
Example 3
The electrochromic device was prepared as in example 1, except that: 1mL of water and 21mmol of lithium bis (trifluoromethanesulfonylimide) (TFSILi) are fully mixed at 60 ℃ for 6 hours under stirring, and the obtained high-concentration water system electrolyte is 21mol/L of an aqueous solution of TFSILi; the performance of the electrochromic device obtained based on the high-concentration aqueous electrolyte (21 mol/L aqueous solution of TFSILI) is basically the same as that of the electrochromic device obtained in the example 1, the device is blue when the neutral state is between 0.2 and 0V, after the voltage is applied to the device and the device is changed from blue to transparent, the absorption peak at 610nm is obviously reduced, and the absorption intensity in the near infrared wavelength range (more than 800 nm) is increased. The optical contrast at 610nm is-43%, and the optical contrast at 1500nm is-22%.
Example 4
(1) 1mL of water and 18mmol of lithium bis (trifluoromethanesulfonylimide) (TFSILi) are stirred at 40 ℃ for 4 hours and fully mixed, and the obtained high-concentration water system electrolyte is 18mol/L of aqueous solution of TFSILi;
(2) spraying a P3HT solution on a first electrode substrate (an anode substrate, ITO glass), and drying to prepare an organic electrochromic layer;
(3) coating sealant on the surface of the first electrode substrate uncovered around the organic electrochromic layer, and reserving an injection port;
(4) covering a second electrode substrate (cathode substrate, ITO glass) above the organic electrochromic layer and attaching the second electrode substrate to the sealant, wherein a cavity is formed between the second electrode substrate and the organic electrochromic layer;
(5) and injecting the prepared aqueous solution of 18mol/L TFSILi into the cavity, and then sealing the injection hole by using a sealant to obtain the electrochromic device based on the high-concentration aqueous electrolyte.
CV curves of the electrochromic device based on the high-concentration aqueous electrolyte prepared in the example are shown in FIG. 5, which shows that the electrochromic device can maintain good oxidation-reduction stability at different scanning speeds, the oxidation potential of P3HT is-0.25V, and the reduction potential is-0.75V. Ultraviolet visible absorption spectra of the electrochromic device based on the high-concentration aqueous electrolyte prepared in the embodiment are shown in fig. 6, when the electrochromic device is in a neutral state of-0.2V-0V, the device is purple red, and after the electrochromic device is applied with a voltage of 1.6V, the device is changed from purple red into transparent color; at 1.6V, the absorption peak at 530nm almost disappeared, and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. The transmittance change at different wavelengths of the electrochromic device based on the high concentration aqueous electrolyte prepared in this example is shown in fig. 7, and it can be seen from fig. 7a that the optical contrast at 530nm is 43.02% and from fig. 7b that the optical contrast at 1500nm is 22.48%.
Example 5 an electrochromic device was prepared as in example 4, except that: 1mL of water and 21mmol of lithium bis (trifluoromethanesulfonylimide) (TFSILi) are fully mixed at 60 ℃ for 6 hours under stirring, and the obtained high-concentration water system electrolyte is 21mol/L of an aqueous solution of TFSILi; the electrochromic device obtained based on a high concentration aqueous electrolyte (21 mol/L aqueous solution of TFSILI) performed substantially the same as example 4, the device faded from purple to substantially colorless, and the absorption peak at 530nm almost disappeared and the absorption intensity in the near infrared wavelength range (> 800 nm) increased when a voltage of 1.6V was applied. At 1.6V, the optical contrast at 530nm is 43% and the optical contrast at 1500nm is 20%.
Example 6
The electrochromic device was prepared as in example 4, except that: 1mL of water and 18mmol of lithium Trifluoromethanesulfonate (TFLi) are fully mixed at 50 ℃ for 4 hours under stirring, and the obtained high-concentration water-based electrolyte is an aqueous solution of 18mol/L TFLi; the electrochromic device obtained on the basis of the high concentration aqueous electrolyte (aqueous solution of 18mol/L TFLi) exhibited substantially the same performance as in example 4, the device was discolored from purple to substantially colorless, and when a voltage of 1.6V was applied, the absorption peak at 530nm almost disappeared and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. At 1.6V, the optical contrast at 530nm is-43%, and the optical contrast at 1500nm is-20%.
Example 7
The electrochromic device was prepared as in example 4, except that: 1mL of water and 14mmol of lithium Trifluoromethanesulfonate (TFLi) are fully mixed at 25 ℃ for 2 hours under stirring, and the obtained high-concentration water-based electrolyte is 14mol/L of an aqueous solution of TFLi; the electrochromic device obtained on the basis of a high concentration aqueous electrolyte (14 mol/L aqueous solution of TFLi) exhibited substantially the same performance as in example 4, the device was discolored from a purple color to substantially colorless, and when a voltage of 1.6V was applied, the absorption peak at 530nm disappeared and the absorption intensity in the near infrared wavelength range (> 800 nm) increased. At a voltage of 1.6V, the optical contrast at 530nm is 43% and the optical contrast at 1500nm is 20%.
Comparative example 1
The electrochromic device was prepared as in example 1, except that: 1mL of water was mixed with 5mmol of lithium perchlorate (LiClO)4) The mixture was thoroughly mixed at 25 ℃ with stirring for 2 hours to obtain an aqueous electrolyte of 5mol/L LiClO4An aqueous solution of (a); based on aqueous electrolyte (5 mol/L LiClO)4Aqueous solution of (1) toThe transmittance change of the prepared electrochromic device at 1500nm is shown in fig. 8, and the optical contrast of the device at 1500nm is only 8%.
Comparative example 2
The electrochromic device was prepared as in example 4, except that: 1mL of water and 22mmol of lithium Trifluoromethanesulfonate (TFLi) are fully mixed at 60 ℃ for 6 hours under stirring, and the obtained water-based electrolyte is 22mol/L of TFSILi aqueous solution; the aqueous electrolyte is in a semi-solid state at room temperature, and the conductivity is reduced; the electrochromic properties of the electrochromic device obtained on the basis of an aqueous electrolyte (22 mol/L of an aqueous solution of tfsii) were poor, and the transmittance change at different wavelengths of the test device at 50 ℃ is shown in fig. 9, with an optical contrast of 22% at 1500nm, but only 20% at 610 nm.
In conclusion, the high-concentration aqueous electrolyte (13-21 mol/L aqueous solution containing lithium fluoride) is used for replacing the traditional low-concentration aqueous electrolyte for the electrochromic device based on the high-concentration aqueous electrolyte constructed by the organic electrochromic device, so that the defects of short service life, narrow working window, easy volatilization of organic solvent-based electrolyte, high toxicity and the like of the organic electroluminescent device caused by the damage of the traditional low-concentration aqueous electrolyte to the organic electrochromic layer are overcome, and the special high contrast in the near infrared region is realized under the condition of ensuring the high contrast in the visible region; the electrochromic device based on the high-concentration water system electrolyte has the advantages of long service life, quick response and good memory, and has guiding significance for the application of the high-concentration water system electrolyte in the fields of electrochromic display, intelligent windows, military camouflage and the like. The electrochromic device based on the high-concentration water system electrolyte has a simple preparation process, and is beneficial to realizing industrial production and application; the optical contrast, the optical memory and the color conversion rate of the electrochromic device in the near infrared region can be adjusted by controlling the concentration of the high-concentration water-based electrolyte.
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 based on a high-concentration aqueous electrolyte, comprising: the electrode comprises a first electrode substrate, an organic electrochromic layer positioned on the first electrode substrate, and a second electrode substrate positioned above the organic electrochromic layer, wherein a cavity is formed between the organic electrochromic layer and the second electrode substrate, and high-concentration aqueous electrolyte is filled in the cavity and is aqueous solution of fluorine-containing lithium salt with the concentration of 13-21 mol/L;
the second electrode substrate is connected with the surface of the first electrode substrate which is not covered with the organic electrochromic layer through a sealant.
2. The high-concentration aqueous electrolyte-based electrochromic device according to claim 1, characterized in that the fluorine-containing lithium salt is selected from one or more of lithium bistrifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bistrifluorosulfonylimide.
3. The high-concentration aqueous electrolyte-based electrochromic device according to claim 1, characterized in that the organic electrochromic layer material is TQ1 or P3 HT.
4. The high-concentration aqueous electrolyte-based electrochromic device according to claim 1, wherein the first and second electrode substrates are independently selected from one of ITO glass, PET/ITO, PDMS/Ag nanowires.
5. A method for preparing an electrochromic device based on a high-concentration aqueous electrolyte according to any one of claims 1 to 4, comprising the steps of:
A. preparing an organic electrochromic layer on a first electrode substrate;
B. coating a sealant on the surface of the first electrode substrate, which is not covered with the organic electrochromic layer, and reserving an injection port;
C. covering a second electrode substrate above the organic electrochromic layer and attaching the second electrode substrate to the sealant, wherein a cavity is formed between the second electrode substrate and the organic electrochromic layer;
D. a highly concentrated aqueous electrolyte is added to the cavity from the injection port, and the injection port is then sealed with a sealant.
6. The method for preparing an electrochromic device based on a high-concentration aqueous electrolyte according to claim 5, wherein in the step A, the method for preparing the organic electrochromic layer is selected from one of spray coating, electrochemical deposition and spin coating.
7. The method for preparing an electrochromic device based on a high-concentration aqueous electrolyte according to claim 6, wherein the spraying specifically comprises: dissolving the organic electrochromic layer material in an organic solvent, spraying the organic electrochromic layer material on the surface of the first electrode substrate, and drying; the organic solvent is chloroform or chlorobenzene.
8. The method for preparing an electrochromic device based on a high-concentration aqueous electrolyte according to claim 5, wherein in step D, the method for preparing a high-concentration aqueous electrolyte comprises the steps of: and mixing the deionized water with the fluorine-containing lithium salt to form the high-concentration aqueous electrolyte.
9. The method for producing a high-concentration aqueous electrolyte-based electrochromic device according to claim 8, wherein the mixing temperature is 25 to 60 ℃.
10. The method for producing an electrochromic device based on a high-concentration aqueous electrolyte according to claim 8, wherein the mixing time is 2 to 6 hours.
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