Electrochromic material, electrochromic device and application thereof

Abstract

The invention relates to the field of electrochromism, and discloses an electrochromism material, an electrochromism device and application of the electrochromism material and the electrochromism device. The electrochromic material is prepared from a copolymer of arylamine and thiophene monomers, and the electrochromic material which is transparent in a neutral state, colored in a doped state and high in optical contrast ratio is achieved by adjusting the positions and types of substituent groups on the arylamine and the thiophene monomers. When the electrochromic material is in a neutral state, the absorption initial wavelength is smaller than or equal to 480 nm, preferably smaller than or equal to 420 nm, the bright-state transmittance under visible light is larger than or equal to 60%, and the electrochromic material is in a transparent state and even colorless; and light absorption in different wavelength ranges can be realized in a doping state (oxidation state), so that various dark-state colors such as purple, red, brown, blue and black can be realized. And the dark state (doped state) transmittance under visible light is less than or equal to 15%, so that high optical contrast can be realized, the optical contrast is greater than or equal to 50%, and the requirements of the fields of intelligent automobiles, 3C and the like on a wider color change range are met.

Description

Technical Field

[0001] This application relates to the field of electrochromism, specifically to a color-changing material, an electrochromic device, and its applications. Background Technology

[0002] Electrochromism (EC) refers to the phenomenon where a material undergoes a reversible change in color or transparency when a voltage is applied. This change is caused by a redox reaction resulting from the injection or extraction of charge. It enables reversible and highly stable changes in transmission / absorption spectra and tunable colors between doped and undoped states, demonstrating significant application potential in various fields such as smart windows, automotive anti-glare rearview mirrors, digital signage, displays, and electronic paper.

[0003] Conjugated polymers are considered ideal materials for fabricating electrochromic devices (ECDs) due to their unique optical properties, such as tunable color, high optical contrast, ease of processing, and good long-term stability. These materials can achieve reversible color changes from neutral to doped states under the influence of an electric field, providing broad application prospects for electrochromic technology. Current research focuses on developing polymer ECDs capable of achieving color changes from saturated colored states to high-transmittance states, especially electrochromic polymers (ECPs) capable of achieving black to transmissive states; these materials are beginning to move towards commercial applications.

[0004] However, neutral-state colored electrochromic polymers (such as the black-to-transmittance type mentioned above) suffer from problems such as low transmittance in the doped state (faded state) and insufficient device contrast. These problems limit the performance of these materials in certain demanding applications.

[0005] In recent years, novel electrochromic polymers with neutral transparency and doped color have gradually attracted attention and research from the academic community due to their advantages such as high contrast. For example, Mario Leclerc et al. synthesized a copolymer containing 4-butyltriphenylamine (BuTPA) via the Suzuki-Miyaura coupling reaction and applied it to electrochromic devices, achieving reversible color changes from light yellow to green and from transparent to khaki. Lin Jin et al. designed carbazole-thiophene monomers with different triphenylamine substituents and studied their electrochemical and electrochromic properties after electropolymerization. Among them, the P(DTC-TPA) film exhibited four color changes: brown-green, blue-gray, blue, and purple-black.

[0006] However, most conjugated polymers currently exhibit colored states, such as blue, yellow, and green, in their neutral state, resulting in low transmittance (<70%) and a narrow color range in their transparent state, making it difficult to meet the needs of high-transmittance applications such as smart windows and transparent displays. Furthermore, achieving dark colors (especially black) in the oxidized state also faces challenges, as black requires simultaneous coverage of a wide range of light absorption wavelengths, and currently, no breakthrough has been achieved in enabling a single polymer to transition from neutral transparency to black.

[0007] Therefore, developing novel neutral, colorless, transparent, and transmissive electrochromic polymers that can be converted to black is a problem that needs to be solved. Summary of the Invention

[0008] The first objective of this invention is to provide an electrochromic material that is neutrally transparent, doped and colored, and has high optical contrast. The second objective of this invention is to provide an electrochromic device.

[0009] To achieve the above-mentioned objectives, this application adopts the following technical solution:

[0010] This application provides an electrochromic material in a first aspect, comprising a polymer having the structure shown in general formula (1):

[0011]

[0012] In general formula (1), A has the structure shown in general formula (2):

[0013]

[0014] B is selected from at least one of the structures shown in general formula (3), general formula (4), and general formula (5), wherein the structures shown in general formula (3), general formula (4), and general formula (5) are:

[0015]

[0016] In the general formula (1), n ​​is an integer equal to or greater than 1; r and s represent mole fractions;

[0017] In the general formula (2), Ar1 and Ar2 are independently represented as substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted 5-30 heteroarylene, respectively.

[0018] In the general formula (2), R is selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 alkoxyalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C4-C30 aminoalkyl, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkylamino, substituted or unsubstituted C5-C 30 Cycloalkylalkylamino, substituted or unsubstituted C5-C30 cycloalkylalkyl, substituted or unsubstituted C5-C30 cycloalkylalkoxy, substituted or unsubstituted C1-C30 heterocyclic, substituted or unsubstituted C1-C30 heterocyclic alkoxy, substituted or unsubstituted C1-C30 heterocyclic amino, substituted or unsubstituted C5-C30 heterocyclic alkylamino, substituted or unsubstituted C3-C30 heterocyclic alkyl, substituted or unsubstituted C1-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylalkyl;

[0019] In the general formulas (3), (4), and (5), R1-R6 are independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 5-30 heteroaryl.

[0020] When Ar1 and Ar2 are unsubstituted C6-C30 arylene groups, B contains at least general formula (4), and at least one of R3 and R4 in general formula (4) is not hydrogen.

[0021] Further, in the general formula (2), R is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C3-C30 alkoxyalkyl.

[0022] Furthermore, A is selected from one of the general formulas (A-1), (A-2), or (A-3):

[0023]

[0024] Both n and m represent the quantity of R'. In the general formula (A-1), n ​​is selected from 1 to 4; in the general formula (A-2), n is selected from 1 to 2; in the general formula (A-3), n is selected from 1 to 2 and m is selected from 1 to 4.

[0025] R' can be independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 5-30 heteroaryl. Adjacent R' groups can be linked to form a ring.

[0026] Furthermore, the general formulas (A-1), (A-2), and (A-3) are respectively:

[0027]

[0028] In the general formula (A-1), R' represents R1 to R8;

[0029] In the general formula (A-2), R' represents R1 to R4;

[0030] In the general formula (A-3), R' represents R1 to R6.

[0031] Furthermore, A is selected from one of the following structural formulas:

[0032]

[0033]

[0034] R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently represented as halogens, substituted or unsubstituted C1-30 alkyl groups, and substituted or unsubstituted C1-30 alkoxy groups, respectively.

[0035] Furthermore, the polymer is selected from any one of the following structural formulas:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] Furthermore, it also includes a conductive material selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, silver nanowires, graphene, carbon nanotubes, silver nanoparticle ink, and organic conductive polymers.

[0043] Furthermore, it also includes a doping material selected from at least one of Lewis acids and Brønsted acids.

[0044] Further, the Lewis acid is selected from at least one of aluminum trichloride, ferric trichloride, boron trifluoride, boron tribromide, tris(pentafluorophenyl)borane, triphenylane, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 7,7,8,8-tetracyano-p-benzodiquinone dimethane, and phosphorus pentachloride;

[0045] The Brønsted acid is selected from at least one of bis(trifluoromethanesulfonyl)imide, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0046] Furthermore, in a neutral state, the electrochromic material absorbs an initiation wavelength ≤480nm.

[0047] Furthermore, in a neutral state, the electrochromic material absorbs an initiation wavelength ≤420nm.

[0048] In a second aspect, this application provides an electrochromic device, including...

[0049] First electrode;

[0050] Second electrode: positioned relative to the first electrode;

[0051] The electrochromic material described above is disposed on the first electrode and located between the first electrode and the second electrode;

[0052] Solid electrolyte: disposed between the electrochromic material and the second electrode;

[0053] Charge storage layer: disposed between the solid electrolyte and the second electrode.

[0054] In a third aspect, this application provides the application of the aforementioned electrochromic device, which is used in automobile windows, anti-glare rearview mirrors, 3C products, building glass curtain walls, and eyeglasses.

[0055] Compared with the prior art, the advantages of the present invention are as follows: The technical solution of the present invention is a copolymer of aromatic amine and thiophene monomers. By adjusting the position and type of substituent groups on the aromatic amine and thiophene monomers, an electrochromic material with neutral transparency, doped color and high optical contrast can be achieved.

[0056] The electrochromic material of this invention, in its neutral state, has an absorption initiation wavelength ≤480nm, preferably ≤420nm, and a bright state transmittance of ≥60% under visible light, exhibiting a transparent state, or even reaching colorless. In its doped (oxidized) state, it can achieve light absorption across different wavelength ranges, thus realizing a variety of dark states such as purple, red, brown, blue, and black. Furthermore, the dark state (doped) transmittance under visible light is ≤15%, thereby achieving high optical contrast, ≥50%, meeting the requirements of smart cars, 3C products, and other fields for a wider range of color changes. Attached Figure Description

[0057] Figure 1 This is a CV potential value detection graph for Example 2.

[0058] Figure 2 The transmittance spectra are for the neutral and oxidized states in Example 2.

[0059] Figure 3 The absorbance spectra are for the neutral and oxidized states in Example 2.

[0060] Figure 4 This is a CV potential value detection graph for Example 4.

[0061] Figure 5 The transmittance spectra are for the neutral and oxidized states in Example 4.

[0062] Figure 6 The absorbance spectra are for the neutral and oxidized states in Example 4.

[0063] Figure 7 This is a CV potential value detection graph from Example 7.

[0064] Figure 8 The transmittance spectra are for the neutral and oxidized states in Example 7.

[0065] Figure 9 The absorbance spectra are for the neutral and oxidized states in Example 7. Detailed Implementation

[0066] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0067] This invention provides 14 embodiments of electrochromic materials. Some of the monomers required for the polymer synthesis reaction in these embodiments are commercially available products, while the remainder are self-made by the applicant. The monomers required for the polymer synthesis reaction are listed in Table 1. The raw materials required for synthesizing the monomers include: Pd2(dba)3, Pd(OAc)2, 1,1-bis(diphenylphosphine)ferrocene (Dppf), 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (Xantphos), 2-bromo-5-iodotoluene, 4-bromophenylaniline, 3-fluoro-4-bromoiodobenzene, 1-bromo-4-iodonaphthalene, 2-bromo-5-iodophenol, bromohexane, 1-bromo-2-(2-methoxyethoxy)ethane, cuprous iodide, sodium tert-butoxide, toluene, xylene, tetrahydrofuran, and ethyl acetate, all of which are commercially available products.

[0068] Table 1. Monomers required for the synthesis reaction of electrochromic materials

[0069]

[0070]

[0071]

[0072] Preparation example: Preparation of monomers A001-A008

[0073] Preparation Example 1: Synthesis of Monomer A001

[0074] Experimental procedure: Add 500 ml xylene, 2-bromo-5-iodotoluene (70.15 g, 236.23 mmol), aniline (10 g, 107.38 mmol), cuprous iodide (4.09 g, 21.48 mmol), and sodium tert-butoxide (30.96 g, 322.13 mmol) to a 1 L three-necked flask, stir and heat to reflux, and react for 20 h.

[0075] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 35.6 g of white solid A001 with a purity of 97.36% and a yield of 76.89%. Elemental analysis (molecular formula C20H17Br2N): Theoretical values: C, 55.71; H, 3.97; Br, 37.06; N, 3.25; Measured values: C, 55.70; H, 3.97; Br, 37.07; N, 3.25. ESI-MS (m / z) (M+): Theoretical value: 430.97; Measured value: 432 (M+H+).

[0076] Preparation Example 2: Synthesis of Monomer A002

[0077] Experimental procedure: Add 500 ml of toluene, 2-bromo-5-iodotoluene (14.36 g, 48.36 mmol), 4-bromophenylaniline (10 g, 40.30 mmol), Pd(OAc)2 (0.18 g, 0.81 mmol), Xantphos (0.93 g, 1.61 mmol), and sodium tert-butoxide (7.75 g, 80.61 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 h.

[0078] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 11.2 g of a white solid, A002, with a purity of 98.38% and a yield of 66.62%. Elemental analysis (molecular formula C19H15Br2N): Theoretical values: C, 54.71; H, 3.62; Br, 38.31; N, 3.36; Measured values: C, 54.70; H, 3.62; Br, 38.32; N, 3.36. ESI-MS (m / z) (M+): Theoretical value: 416.96; Measured value: 418 (M+H+).

[0079] Preparation Example 3: Synthesis of Monomer A003

[0080] Experimental procedure: Add 500 ml of toluene, 3-fluoro-4-bromoiodobenzene (14.55 g, 48.36 mmol), 4-bromophenylaniline (10 g, 40.30 mmol), Pd2(dba)3 (1.85 g, 2.02 mmol), Dppf (2.24 g, 4.03 mmol), and sodium tert-butoxide (7.75 g, 80.61 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 h.

[0081] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 12.3 g of white solid A003 with a purity of 97.97% and a yield of 72.47%. Elemental analysis (molecular formula C18H12Br2FN): Theoretical values: C, 51.34; H, 2.87; Br, 37.95; F, 4.51; N, 3.33; Measured values: C, 51.33; H, 2.87; Br, 37.96; F, 4.51; N, 3.33. ESI-MS (m / z) (M+): Theoretical value: 420.93; Measured value: 422 (M+H+).

[0082] Preparation Example 4: Synthesis of Monomer A004

[0083] Experimental procedure: Add 500 ml of toluene, 1-bromo-4-iodonaphthalene (16.10 g, 48.36 mmol), 4-bromophenylaniline (10 g, 40.30 mmol), Pd2(dba)3 (1.85 g, 2.02 mmol), Dppf (2.24 g, 4.03 mmol), and sodium tert-butoxide (7.75 g, 80.61 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 h.

[0084] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 13.5 g of a yellow oily liquid, A004, with a purity of 93.04% and a yield of 73.92%. Elemental analysis (molecular formula C22H15Br2N): Theoretical values: C, 58.31; H, 3.34; Br, 35.26; N, 3.09; Measured values: C, 58.30; H, 3.34; Br, 35.27; N, 3.09. ESI-MS (m / z) (M+): Theoretical value: 452.96; Measured value: 454 (M+H+).

[0085] Preparation Example 5: Synthesis of Monomer A005

[0086] Experimental Step 1: Add 500 ml of toluene, 4-bromo-3-methyl-aniline (10 g, 48.36 mmol), 2-bromo-5-iodotoluene (19.15 g, 64.50 mmol), Pd(OAc)2 (0.24 g, 1.07 mmol), Xantphos (1.24 g, 2.15 mmol), and sodium tert-butoxide (10.33 g, 107.50 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 12 h.

[0087] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. The organic phase was purified by column chromatography to obtain 12.2 g of yellow oily liquid intermediate A005 with a purity of 94.52% and a yield of 63.93%.

[0088] Experimental Step 2: Add 100 ml of tetrahydrofuran, A005 intermediate (10 g, 28.16 mmol), 1-bromo-2-(2-methoxyethoxy)ethane (7.73 g, 42.24 mmol), and sodium tert-butoxide (5.41 g, 56.33 mmol) to a 250 ml three-necked flask, stir and heat to reflux, and react for 4 h.

[0089] After the reaction was complete, the mixture was cooled to room temperature, diluted with water, extracted with ethyl acetate, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 8.7 g of a pale yellow solid, A005, with a purity of 96.81% and a yield of 67.57%. Elemental analysis (molecular formula C19H23Br2NO2): Theoretical values: C, 49.91; H, 5.07; Br, 34.95; N, 3.06; O, 7.00; Measured values: C, 49.90; H, 5.07; Br, 34.96; N, 3.06; O, 7.00. ESI-MS (m / z) (M+): Theoretical value: 457.01; Measured value: 458 (M+H+).

[0090] Preparation Example 6: Synthesis of Monomer A006

[0091] Experimental Step 1: Add 500 ml of tetrahydrofuran, 2-bromo-5-iodophenol (50 g, 167.28 mmol), bromohexane (41.42 g, 250.92 mmol), and sodium tert-butoxide (32.15 g, 334.55 mmol) to a 1 L three-necked flask, stir and heat to reflux, and react for 4 h.

[0092] After the reaction was complete, the mixture was cooled to room temperature, diluted with water, extracted with ethyl acetate, concentrated to dryness, and purified by column chromatography to obtain 51.3 g of white solid A006 intermediate with a purity of 97.21% and a yield of 80.06%.

[0093] Experimental Step 2: Add 500 ml of toluene, A006 intermediate (45.25 g, 118.12 mmol), aniline (5 g, 53.69 mmol), Pd2(dba)3 (2.46 g, 2.68 mmol), Dppf (2.99 g, 5.37 mmol), and sodium tert-butoxide (10.32 g, 107.38 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 4 h.

[0094] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 21.7 g of a white solid, A006, with a purity of 97.34% and a yield of 66.98%. Elemental analysis (molecular formula C28H33Br2NO6): Theoretical values: C, 52.60; H, 5.20; Br, 24.99; N, 2.19; O, 15.01; Measured values: C, 52.59; H, 5.20; Br, 25.00; N, 2.19; O, 15.01. ESI-MS (m / z) (M+): Theoretical value: 639.07; Measured value: 640 (M+H+).

[0095] Preparation Example 7: Synthesis of Monomer A007

[0096] Experimental procedure: 2000 ml of toluene, 2,5-dibromo-3,4-dimethylthiophene (191.33 g, 236.23 mmol), aniline (30 g, 322.13 mmol), Pd2(dba)3 (14.75 g, 16.11 mmol), Dppf (17.92 g, 32.21 mmol), and sodium tert-butoxide (61.92 g, 644.27 mmol) were added to a 3 L three-necked flask. The mixture was stirred and heated to reflux, and the reaction was allowed to proceed for 16 h.

[0097] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 105.72 g of white solid A007 with a purity of 95.48% and a yield of 69.64%. Elemental analysis (molecular formula C18H17Br2NS2): Theoretical values: C, 45.88; H, 3.64; Br, 33.91; N, 2.97; S, 13.61; Measured values: C, 45.87; H, 3.64; Br, 33.92; N, 2.97; S, 13.61. ESI-MS (m / z) (M+): Theoretical value: 297.74; Measured value: 299 (M+H+).

[0098] Preparation Example 8: Synthesis of Monomer A008

[0099] Experimental procedure: Add 2000 ml of toluene, A015 (272.23 g, 322.13 mmol), aniline (30 g, 322.13 mmol), Pd2(dba)3 (14.75 g, 16.11 mmol), Dppf (17.92 g, 32.21 mmol), and sodium tert-butoxide (61.92 g, 644.27 mmol) to a 3 L three-necked flask, stir and heat to reflux, and react for 8 h.

[0100] After the reaction was complete, the mixture was cooled to room temperature, washed with water, and the organic phase was concentrated to dryness. Purification by column chromatography yielded 90.84 g of a light yellow solid, A008, with a purity of 95.75% and a yield of 40.31%. Elemental analysis (molecular formula C30H37Br2NO4S2): Theoretical values: C, C, 51.51; H, 5.33; Br, 22.84; N, 2.00; O, 9.15; S, 9.17; Measured values: C, 51.51; H, 5.33; Br, 22.84; N, 2.00; O, 9.15; S, 9.17. ESI-MS (m / z) (M+): Theoretical value 1244.89, measured value 1246 (M+H+).

[0101] The chemical structural formulas of the polymers in the 14 examples and the monomers used to synthesize the polymers are shown in Table 2. Other raw materials required for synthesis include: potassium carbonate (K2CO3), pentyl acid (PivOH), palladium acetate (Pd(OAc)2), dimethylacetamide (DMAC), and methanol, all of which are commercially available products.

[0102] Table 2. Polymers and monomers used to synthesize the polymers in the embodiments of the present invention.

[0103]

[0104]

[0105]

[0106]

[0107]

[0108] Example: Preparation of polymers P001-P014

[0109] Example 1

[0110] Example 1: Preparation of polymer P001

[0111] The preparation steps are as follows:

[0112] 1) Under a nitrogen atmosphere, monomers A001 (1 eq), A009 (1 eq), K2CO3 (2.6 eq), PivOH (0.3 eq), and Pd(OAc)2 (0.02 eq) were sequentially added into a dry, clean reactor that had been purged with nitrogen.

[0113] 2) Add the nitrogen-degassed solvent dimethylacetamide (DMAC) into the reactor; the feeding is now complete.

[0114] 3) Turn on the stirrer in the reactor and stir for 10 minutes. Then heat the reaction solution to 140°C and maintain the temperature for 5 hours.

[0115] 4) After the reaction is complete, cool to room temperature and add an appropriate amount of DMAC while stirring to dissolve all the undissolved polymer;

[0116] 5) Filter the dissolved reaction solution to remove inorganic salts and obtain the filtrate;

[0117] 6) Then the filtrate is added dropwise to 3 to 5 times its volume of methanol, the precipitate is collected and filtered to obtain the crude polymer;

[0118] 7) Wash the crude polymer with deionized water at 50℃ 5-10 times, then wash with methanol 2-3 times, and dry in a vacuum drying oven at 70℃ for 24 hours to obtain polymer P001.

[0119] The yield of polymer P001 was 76.5%.

[0120] Example 2: Preparation of polymer P002

[0121] The preparation method of polymer P002 is the same as in Example 1, except that monomer raw material A001 is replaced with A002.

[0122] The yield of polymer P002 was 73.3%.

[0123] Example 3: Preparation of polymer P003

[0124] The preparation method of polymer P003 is the same as in Example 1, except that the monomer raw material A001 is replaced with A003.

[0125] The yield of polymer P003 was 81.3%.

[0126] Example 4: Preparation of polymer P004

[0127] The preparation method of polymer P004 is the same as in Example 1, except that monomer raw material A009 is replaced with A012.

[0128] The yield of polymer P004 was 75.7%.

[0129] Example 5: Preparation of polymer P005

[0130] The preparation method of polymer P005 is the same as in Example 1, except that monomer raw material A001 is replaced with A002 and A009 is replaced with A012.

[0131] The yield of polymer P005 was 78.6%.

[0132] Example 6: Preparation of polymer P006

[0133] The preparation method of polymer P006 is the same as in Example 1, except that the monomer raw material A001 is replaced with A004.

[0134] The yield of polymer P006 was 68.5%.

[0135] Example 7: Preparation of polymer P007

[0136] The preparation method of polymer P007 is the same as in Example 1, except that monomer raw material A001 is replaced with A010 and monomer raw material A009 is replaced with A014.

[0137] The yield of polymer P007 was 71.4%.

[0138] Example 8: Preparation of polymer P008

[0139] The preparation method of polymer P008 is the same as in Example 1, except that monomer raw material A001 is replaced with A011 and monomer raw material A009 is replaced with A014.

[0140] The yield of polymer P008 was 74.5%.

[0141] Example 9: Preparation of polymer P009

[0142] The preparation method of polymer P009 is the same as in Example 1, except that monomer raw material A001 is replaced with A002 and monomer raw material A009 is replaced with A013.

[0143] The yield of polymer P009 was 57.1%.

[0144] Example 10: Preparation of polymer P010

[0145] The preparation method of polymer P010 is the same as in Example 1, except that monomer raw material A001 is replaced with A005.

[0146] The yield of polymer P010 was 82.9%.

[0147] Example 11: Preparation of polymer P011

[0148] The preparation method of polymer P011 is the same as in Example 1, except that monomer raw material A001 is replaced with A006 and monomer raw material A009 is replaced with A014.

[0149] The yield of polymer P011 was 67.5%.

[0150] Example 12: Preparation of polymer P012

[0151] The preparation method of polymer P012 is the same as in Example 1, except that the monomer raw material A001 is replaced with A007.

[0152] The yield of polymer P012 was 58.6%.

[0153] Example 13: Preparation of polymer P013

[0154] The preparation method of polymer P013 is the same as in Example 1, except that monomer raw material A001 is replaced with A008 and monomer raw material A009 is replaced with A014.

[0155] The yield of polymer P013 was 63.2%.

[0156] Example 14: Preparation of polymer P014

[0157] The preparation method of polymer P014 is the same as in Example 2, except that 0.1% of carbon nanotubes by mass of the total polymer are added.

[0158] Performance testing

[0159] The obtained polymers P001-P014 from the examples were prepared into thin films. Specifically, the polymer samples were dissolved in chloroform, spin-coated onto the ITO surface, and dried to obtain the working electrode.

[0160] 1) Cyclic voltammetry (CV) test: The obtained samples were subjected to cyclic voltammetry tests using a Chenhua CHI600E electrochemical workstation. A platinum sheet electrode and an Ag / AgCl electrode were used as the auxiliary electrode and reference electrode, respectively. 0.1 M (mol / L) tetrabutylammonium hexafluorophosphate was dissolved in anhydrous acetonitrile as the supporting electrolyte.

[0161] 2) Transmittance and absorbance tests in neutral and oxidized states: The transmittance and absorption spectra of the polymer film in neutral and oxidized states were tested using ultraviolet-visible absorption spectroscopy.

[0162] 3) Color test: The neutral and oxidized colors of the polymer film were tested using a spectrophotometer.

[0163] 4) Optical contrast: The maximum optical contrast at a specific wavelength within the visible light region.

[0164] Table 3 shows the CV potential values, transmittance in the neutral state and the oxidized state of Examples 1-14. They all exhibited high transparency in the neutral state and purple, red, brown, green or black in the oxidized state.

[0165] Examples 2, 3, and 7 involved quantitative color measurements (color testing): To accurately assess color characteristic changes during the electrochemical conversion process, the CIE 1976 L*a*b* color standard was used for quantitative color measurement. CIE 1976 is the color space adopted by the International Commission on Illumination (CIE) in 1976, where L* represents luminance (0 to 100), and a* and b* are the hue and chromaticity values, respectively. More specifically, positive and negative a* values ​​correspond to red and green hues, respectively, and positive and negative b* values ​​represent yellow and blue chromaticity. The test results are shown in Table 4.

[0166] The oxidation peak potential of Example 2 (P002) is approximately 1.12V. Figure 1 The overall transmittance in the visible light region under neutral conditions is above 80%, indicating that it is transparent under neutral conditions. The optical contrast ratio at 616 nm is 74.95%. Figure 2 The initial absorption wavelength in the neutral state is approximately 450 nm, with color coordinates L* = 93.75, a* = -12.84, and b* = 35.78, exhibiting a slightly yellow tint.

[0167] In its oxidized state, it exhibits an absorption peak at 560 nm and another, broader peak at approximately 800-1100 nm. Its color coordinates are L* = 47.17, a* = 2.39, b* = -9.60, resulting in a grayish-blue color. Figure 3 ).

[0168] The oxidation peak potential of Example 3 (P003) is approximately 1.11V. Figure 4 The overall transmittance in the visible light region under neutral conditions is above 80%, indicating that it is transparent under neutral conditions. The optical contrast ratio at 586 nm is 83.70%. Figure 5 The initial absorption wavelength in the neutral state is approximately 460 nm, with color coordinates L* = 93.72, a* = -17.03, and b* = 52.65, exhibiting a slightly yellow tint.

[0169] In its oxidized state, it exhibits an absorption peak at 600 nm and another, broader peak above 1100 nm. Its color coordinates are L* = 39.97, a* = -12.6, b* = 0.54, indicating a green color. Figure 6 ).

[0170] The oxidation peak potential of Example 7 (P007) is approximately 1.05V. Figure 7 The overall transmittance in the visible light region under neutral conditions is above 80%, indicating that it is transparent under neutral conditions. The optical contrast ratio at 529 nm is 83.84%. Figure 8 In the neutral state, the initial absorption wavelength is approximately 419 nm, with color coordinates L* = 94.17, a* = -1.47, and b* = 6.15, exhibiting complete colorlessness and transparency.

[0171] In its oxidized state, it exhibits an absorption peak at 520 nm and another, broader peak at approximately 800-1100 nm. The color coordinates are L* = 40.27, a* = 14.58, b* = 10.96, resulting in a brownish color. Figure 9 ).

[0172] Table 3 Performance of the polymer films in the examples

[0173] Group CV oxidation potential value / V Neutral transmittance / % Oxidized state transmittance / % Optical contrast ratio / % Example 1 1.04 92.73 10.21 82.52 Example 2 1.12 88.90 13.95 74.95 Example 3 1.11 90.77 7.07 83.70 Example 4 1.08 88.79 8.45 80.34 Example 5 1.15 90.38 7.27 83.11 Example 6 1.04 92.35 9.54 82.81 Example 7 1.05 90.20 6.36 83.84 Example 8 1.07 87.87 12.11 75.76 Example 9 1.01 90.54 8.23 82.31 Example 10 1.03 91.35 10.12 81.23 Example 11 1.13 91.21 14.56 76.65 Example 12 1.11 89.65 12.31 77.34 Example 13 1.07 89.35 9.23 80.12 Example 14 0.91 89.21 10.01 79.2

[0174] Table 4. Colors of the polymer films in neutral and oxidized states in the examples.

[0175]

[0176]

[0177] Application examples

[0178] An electrochromic device, comprising

[0179] First electrode: Tin-doped indium oxide (ITO);

[0180] Second electrode: Indium tin oxide (ITO);

[0181] Electrochromic material (polymer P001 thin film): disposed on the first electrode and located between the first electrode and the second electrode;

[0182] Solid electrolyte: Li+-doped polyethylene oxide (PEO) is placed between the electrochromic material and the second electrode.

[0183] Charge storage layer: V2O5, deposited on the second electrode, positioned between the solid electrolyte and the second electrode.

[0184] The prepared electrochromic devices can be applied to automobile windows, anti-glare rearview mirrors, 3C products, building glass curtain walls, and eyewear.

[0185] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. An electrochromic material, characterized in that, The polymer includes a polymer having the structure shown in general formula (1): In general formula (1), A has the structure shown in general formula (2): B is selected from at least one of the structures shown in general formula (3), general formula (4), and general formula (5), wherein the structures shown in general formula (3), general formula (4), and general formula (5) are: In the general formula (1), n ​​is an integer equal to or greater than 1; r and s represent mole fractions; In the general formula (2), Ar1 and Ar2 are independently represented as substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted 5-30 heteroarylene, respectively. In the general formula (2), R is selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 alkoxyalkyl, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C4-C30 aminoalkyl, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkylamino, substituted or unsubstituted C5-C 30 Cycloalkylalkylamino, substituted or unsubstituted C5-C30 cycloalkylalkyl, substituted or unsubstituted C5-C30 cycloalkylalkoxy, substituted or unsubstituted C1-C30 heterocyclic, substituted or unsubstituted C1-C30 heterocyclic alkoxy, substituted or unsubstituted C1-C30 heterocyclic amino, substituted or unsubstituted C5-C30 heterocyclic alkylamino, substituted or unsubstituted C3-C30 heterocyclic alkyl, substituted or unsubstituted C1-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylalkyl; In the general formulas (3), (4), and (5), R1-R6 are independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 5-30 heteroaryl. When Ar1 and Ar2 are unsubstituted C6-C30 arylene groups, B contains at least general formula (4), and at least one of R3 and R4 in general formula (4) is not hydrogen.

2. The electrochromic material according to claim 1, characterized in that, In the general formula (2), R is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C3-C30 alkoxyalkyl.

3. The electrochromic material according to claim 1, characterized in that, The A is selected from one of the general formulas (A-1), (A-2), or (A-3): Both n and m represent the quantity of R'. In the general formula (A-1), n ​​is selected from 1 to 4; in the general formula (A-2), n is selected from 1 to 2; in the general formula (A-3), n is selected from 1 to 2 and m is selected from 1 to 4. R' can be independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 5-30 heteroaryl. Adjacent R' groups can be linked to form a ring.

4. The electrochromic material according to claim 3, characterized in that, The general formulas (A-1), (A-2), and (A-3) are respectively: In the general formula (A-1), R' represents R1 to R8; In the general formula (A-2), R' represents R1 to R4; In the general formula (A-3), R' represents R1 to R6.

5. The electrochromic material according to claim 4, characterized in that, A is selected from one of the following structural formulas: R1, R2, R3, R4, R5, R6, R7, R8, R9, and R10 are independently represented as halogens, substituted or unsubstituted C1-30 alkyl groups, and substituted or unsubstituted C1-30 alkoxy groups, respectively.

6. The electrochromic material according to claim 5, characterized in that, The polymer is selected from any one of the following structural formulas:

7. The electrochromic material according to claim 1, characterized in that, It also includes conductive materials, which are selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, silver nanowires, graphene, carbon nanotubes, silver nanoparticle ink, and organic conductive polymers.

8. The electrochromic material according to claim 1, characterized in that, It also includes doping materials, which are selected from at least one of Lewis acids and Brønsted acids.

9. The electrochromic material according to claim 8, characterized in that, The Lewis acid is selected from at least one of aluminum trichloride, ferric trichloride, boron trifluoride, boron tribromide, tris(pentafluorophenyl)borane, triphenylane, 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone, 7,7,8,8-tetracyano-p-benzodiquinone dimethane, and phosphorus pentachloride. The Brønsted acid is selected from at least one of bis(trifluoromethanesulfonyl)imide, methanesulfonic acid, and trifluoromethanesulfonic acid.

10. The electrochromic material according to any one of claims 1 to 9, characterized in that, In a neutral state, the absorption initiation wavelength of the electrochromic material is ≤480nm.

11. The electrochromic material according to any one of claims 1 to 9, characterized in that, In a neutral state, the absorption initiation wavelength of the electrochromic material is ≤420nm.

12. An electrochromic device, characterized in that, include First electrode; Second electrode: positioned relative to the first electrode; The electrochromic material according to any one of claims 1 to 11: disposed on the first electrode and located between the first electrode and the second electrode; Solid electrolyte: disposed between the electrochromic material and the second electrode; Charge storage layer: disposed between the solid electrolyte and the second electrode.

13. The application of the electrochromic device according to claim 12, characterized in that, The electrochromic device is used in automobile windows, anti-glare rearview mirrors, 3C products, building glass curtain walls, and eyewear.

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