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. According to the invention, polymers with different chemical structures, such as a combination of arylamine and thiophene fragments or a combination of arylamine, thiophene and carbazole fragments, are prepared, and the electrochromic material which is transparent in a neutral state, colored in a doped state and high in optical contrast ratio is realized by adjusting the positions and types of substituent groups on arylamine, thiophene and carbazole. When the electrochromic material is in a neutral state, the absorption initial wavelength is smaller than or equal to 480 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, so that various dark-state colors such as purple, red, brown and black can be realized. And the dark-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 intelligent automobiles, 3C and other fields on a wider color change range are met.

Description

Technical Field

[0001] This application relates to the field of electrochromism, and more specifically, to an electrochromic 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.

[0006] However, most conjugated polymers currently exhibit colored states, such as blue, yellow, and green, in their neutral state, resulting in low transmittance and a narrow color-changing range in their transparent state. This makes it difficult to meet the requirements of high-transmittance applications such as smart windows and transparent displays. Furthermore, achieving dark colors (especially black) in the oxidized state also presents 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] In a first aspect, this application provides an electrochromic material comprising a polymer, said polymer containing at least three of segments A, B, C, D, and E, and containing at least segments A and B;

[0011] The A and E segments have different chemical structures, and both have the structure shown in general formula (1):

[0012]

[0013] The C segment has the structure shown in general formula (2):

[0014]

[0015] The chemical structures of fragments B and D are different, and each is independently selected from one of the following general formulas (3), (4), and (5):

[0016]

[0017] In the general formula (1), Ar1 and Ar2 are independently represented as substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C5-C30 heteroarylene, respectively.

[0018] In the general formula (2), n represents the number of Rb and Ra, and n is selected from 1 to 3; Ra and Rb are independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl groups, and adjacent Ra or Rb groups can be linked to form a ring;

[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, and substituted or unsubstituted C5-C30 heteroaryl, respectively.

[0020] In the general formulas (1) and (2), R independently represents 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 Substituted C5-C30 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.

[0021] Furthermore, in the general formulas (1) and (2), R is independently represented as a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C1-C30 alkyl, or a substituted or unsubstituted C3-C30 alkoxyalkyl, respectively.

[0022] Furthermore, the polymer is selected from any one or a combination of the following general formulas:

[0023]

[0024] Where n is an integer equal to or greater than 1; w, x, y, z, and u represent mole fractions.

[0025] Further, in general formula (Ⅰ), 0.1≤(w+y):x≤4; in general formula (Ⅱ), 0.1≤w:(x+z)≤4; in general formula (Ⅲ), 0.1≤(w+u):x≤4; in general formula (Ⅳ), 0.1≤(w+u):(x+z)≤4; in general formula (Ⅴ), 0.1≤(w+y):(x+z)≤4; in general formula (VI), 0.1≤(w+y):(x+u)≤4.

[0026] Furthermore, the A segment and E segment are selected from one of the general formulas (A-1), (A-2), or (A-3):

[0027]

[0028] n represents 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.

[0029] 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 C5-C30 heteroaryl. Adjacent R' groups may be linked to form a ring.

[0030] Furthermore, the general formulas (A-1), (A-2), and (A-3) are respectively:

[0031]

[0032] In the general formula (A-1), R' represents R1 to R8;

[0033] In the general formula (A-2), R' represents R1 to R4;

[0034] In the general formula (A-3), R' represents R1 to R6.

[0035] Furthermore, in the general formula (A-1), R2, R3, R6, and R7 are all hydrogen; in the general formula (A-2), R1 and R4 are both hydrogen; and in the general formula (A-3), R2, R3, and R6 are all hydrogen.

[0036] The B fragment is of general formula (5) or a combination thereof, and at least one of R3 and R4 in general formula (5) is a substituted or unsubstituted halogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, or a substituted or unsubstituted C5-C30 heteroaryl.

[0037] Furthermore, the polymer is selected from one of the following general formulas:

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] 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.

[0047] Furthermore, it also includes a doping material selected from at least one of Lewis acids and Brønsted acids.

[0048] 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;

[0049] The Brønsted acid is selected from at least one of bis(trifluoromethanesulfonyl)imide, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0050] Furthermore, in a neutral state, the electrochromic material absorbs an initiation wavelength ≤480nm.

[0051] Furthermore, in a neutral state, the electrochromic material absorbs an initiation wavelength ≤420nm.

[0052] In a second aspect, this application provides an electrochromic device, comprising:

[0053] First electrode;

[0054] Second electrode: positioned relative to the first electrode;

[0055] The electrochromic material described in the first aspect is disposed on the first electrode and located between the first electrode and the second electrode;

[0056] Solid electrolyte: disposed between the electrochromic material and the second electrode;

[0057] Charge storage layer: disposed between the solid electrolyte and the second electrode.

[0058] 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.

[0059] In summary, compared with the prior art, the advantages of the present invention are as follows:

[0060] The different chemical structures of the technical solutions of the present invention, such as polymers composed of aromatic amines and thiophene fragments, or polymers composed of aromatic amines, thiophene, and carbazole fragments, can achieve electrochromic materials with neutral transparency, doped color, and high optical contrast by adjusting the position and type of substituent groups on the aromatic amines, thiophene, and carbazole.

[0061] The electrochromic material of this invention, in its neutral state, has an absorption initiation wavelength ≤480nm 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-state colors such as purple, red, brown, 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

[0062] Figure 1 This is a CV potential value detection graph for Example 3.

[0063] Figure 2 The transmittance spectra are for the neutral and oxidized states in Example 3.

[0064] Figure 3 The absorbance spectra are for the neutral and oxidized states in Example 3.

[0065] Figure 4 This is a CV potential value detection graph for Example 13.

[0066] Figure 5 The transmittance spectra are for the neutral and oxidized states in Example 13.

[0067] Figure 6 The absorbance spectra for the neutral and oxidized states in Example 13 are shown. Detailed Implementation

[0068] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0069] This invention provides 18 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, 1,1-bis(diphenylphosphine)ferrocene (Dppf), Pd(OAc)2, 4,5-bis(diphenylphosphine)-9,9-dimethyloxanthracene (Xantphos), 2-bromo-5-iodotoluene, aniline, 4-bromophenylaniline, 3-fluoro-4-bromoiodobenzene, 1-bromo-4-iodonaphthalene, 2-hexyl-2,3-dihydrothiophene[3,4-B][1,4]dioxin, 3,6-dibromocarbazole, hexane, cuprous iodide, sodium tert-butoxide, N-bromosuccinimide (NBS), toluene, xylene, tetrahydrofuran, and dichloromethane, all of which are commercially available products.

[0070] Table 1. Monomers required for the synthesis reaction of electrochromic materials

[0071]

[0072]

[0073]

[0074]

[0075] Preparation example: Preparation of monomers B01-B08

[0076] Preparation Example 1: Synthesis of Monomer B01

[0077] 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.

[0078] 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 35.6 g of white solid B01 with a purity of 97.36% and a yield of 76.89%.

[0079] Elemental analysis of the structure (molecular formula C) 20 H 17 Br₂N: 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⁺) + ).

[0080] Preparation Example 2: Synthesis of Monomer BO2

[0081] 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.

[0082] 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 11.2 g of white solid BO2 with a purity of 98.38% and a yield of 66.62%.

[0083] Elemental analysis of the structure (molecular formula C) 19 H 15 Br₂N: 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⁺) + ).

[0084] Preparation Example 3: Synthesis of Monomer BO3

[0085] 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.

[0086] 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 12.3 g of white solid BO3 with a purity of 97.97% and a yield of 72.47%.

[0087] Elemental analysis of the structure (molecular formula C) 18 H 12Br2FN): 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) + ).

[0088] Preparation Example 4: Synthesis of Monomer BO4

[0089] 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.

[0090] 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 then purified by column chromatography to obtain 13.5 g of yellow oily liquid BO4 with a purity of 93.04% and a yield of 73.92%.

[0091] Elemental analysis of the structure (molecular formula C) 22 H 15 Br₂N: 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⁺). + ).

[0092] Preparation Example 5: Synthesis of Monomer B05

[0093] Experimental procedure: Add 500 ml of toluene, 3,6-dibromocarbazole (20 g, 61.54 mmol), 2-bromonaphthalene (15.29 g, 73.85 mmol), Pd2(dba)3 (2.82 g, 3.08 mmol), Dppf (3.42 g, 6.15 mmol), and sodium tert-butoxide (11.83 g, 123.08 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 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. The organic phase was purified by column chromatography to obtain 21.73 g of white solid B05 with a purity of 99.14% and a yield of 78.27%.

[0095] Elemental analysis of the structure (molecular formula C)22 H 13 Br₂N): Theoretical values: C, 58.57; H, 2.90; Br, 35.42; N, 3.10; Measured values: C, 58.56; H, 2.90; Br, 35.43; N, 3.10. ESI-MS (m / z) (M⁺): Theoretical value: 450.94; Measured value: 452 (M⁺H⁺). + ).

[0096] Preparation Example 6: Synthesis of Monomer B06

[0097] Experimental procedure: Add 500 ml of tetrahydrofuran, 3,6-dibromocarbazole (20 g, 61.54 mmol), bromohexane (20.32 g, 123.08 mmol), and sodium tert-butoxide (11.83 g, 123.08 mmol) to a 1 L three-necked flask, stir and heat to reflux, and react for 6 h.

[0098] After the reaction was complete, the mixture was cooled to room temperature, washed with water, extracted with dichloromethane, concentrated to dryness, and purified by column chromatography to obtain 19.88 g of white solid B06 with a purity of 98.56% and a yield of 78.95%.

[0099] Elemental analysis of the structure (molecular formula C) 18 H 19 Br₂N: Theoretical values: C, 52.84; H, 4.68; Br, 39.06; N, 3.42; Measured values: C, 52.83; H, 4.68; Br, 39.07; N, 3.42. ESI-MS (m / z) (M⁺): Theoretical value: 408.99; Measured value: 410 (M⁺H) + ).

[0100] Preparation Example 7: Synthesis of Monomer B07

[0101] Experimental procedure: Add 500 ml of toluene, 2,5-dibromo-3,4-dimethylthiophene (26.11 g, 96.73 mmol), 4-bromophenylaniline (20 g, 80.61 mmol), Pd2(dba)3 (3.69 g, 4.03 mmol), Dppf (4.48 g, 8.06 mmol), and sodium tert-butoxide (15.49 g, 161.21 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 h.

[0102] 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 then purified by column chromatography to obtain 11.7 g of yellow oily liquid B07 with a purity of 96.34% and a yield of 33.20%.

[0103] Elemental analysis of the structure (molecular formula C) 18 H 15Br2NS): Theoretical values: C, 49.45; H, 3.46; Br, 36.55; N, 3.20; S, 7.33; Measured values: C, 49.44; H, 3.46; Br, 36.56; N, 3.20; S, 7.33. ESI-MS (m / z)(M+): Theoretical value: 436.93; Measured value: 438 (M+H) + ).

[0104] Preparation Example 8: Synthesis of Monomer B08

[0105] Experimental procedure: Add 500 ml of toluene, B18 (37.16 g, 96.73 mmol), 4-bromophenylaniline (20 g, 80.61 mmol), Pd2(dba)3 (3.69 g, 4.03 mmol), Dppf (4.48 g, 8.06 mmol), and sodium tert-butoxide (15.49 g, 161.21 mmol) to a 1 L three-necked flask. Under nitrogen protection, stir and heat to reflux, and react for 6 h.

[0106] 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 14.8 g of yellow oily liquid B08 with a purity of 97.62% and a yield of 33.30%.

[0107] Elemental analysis of the structure (molecular formula C) 24 H 25 (Br2NO2S): Theoretical values: C, 52.28; H, 4.57; Br, 28.99; N, 2.54; O, 5.80; S, 5.81; Measured values: C, 52.27; H, 4.57; Br, 29.00; N, 2.54; O, 5.80; S, 5.81. ESI-MS (m / z)(M+): Theoretical value: 551.00; Measured value: 552 (M+H) + ).

[0108] The chemical structural formulas of the polymers in the 18 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.

[0109] Table 2. Polymers and monomers used to synthesize the polymers in the embodiments of the present invention.

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116] Example: Preparation of polymers P01-P18

[0117] Example 1: Preparation of polymer PO1

[0118] The preparation steps are as follows:

[0119] 1) Under a nitrogen atmosphere, monomers B01 (0.1 eq), B09 (1 eq), and B15 (0.9 eq) were added into a dry and clean reactor;

[0120] 2) Continue to add K2CO3 (2.6 eq), PivOH (0.3 eq), and Pd(OAc)2 (0.02 eq);

[0121] 3) Add the nitrogen-degassed solvent dimethylacetamide (DMAC) into the reactor, and clean the feeding container three times with DMAC. The cleaning solution is also added into the reactor. The feeding is now complete.

[0122] 4) Turn on the stirrer in the reactor and stir for 10 minutes. Then heat the reaction solution to 170°C and maintain the temperature for 5 hours.

[0123] 5) After the reaction is complete, cool to room temperature and add an appropriate amount of DMAC while stirring to dissolve all the undissolved polymer;

[0124] 6) Filter the dissolved reaction solution to remove inorganic salts and obtain the filtrate;

[0125] 7) 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;

[0126] 8) 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 PO1;

[0127] The yield of polymer P01 was 66.3%.

[0128] Example 2: Preparation of polymer PO2

[0129] The preparation method of polymer PO2 is the same as in Example 1, except that the monomer raw materials are B10 (0.25 eq), B09 (1 eq), and B15 (0.75 eq).

[0130] The polymer PO2 yield was 61.7%.

[0131] Example 3: Preparation of polymer PO3

[0132] The preparation method of polymer PO3 is the same as in Example 1, except that the monomer raw materials are B10 (0.5 eq), B14 (1 eq), and B15 (0.5 eq).

[0133] The yield of polymer PO3 was 69.2%.

[0134] Example 4: Preparation of polymer PO4

[0135] The preparation method of polymer PO4 is the same as in Example 1, except that the monomer raw materials are B14 (0.2 eq), BO2 (1 eq), and BO9 (0.8 eq).

[0136] The yield of polymer PO4 was 55.9%.

[0137] Example 5: Preparation of polymer PO5

[0138] The preparation method of polymer PO5 is the same as in Example 1, except that the monomer raw materials are B14 (0.5 eq), BO2 (1 eq), and B12 (0.5 eq).

[0139] The yield of polymer PO5 was 59.5%.

[0140] Example 6: Preparation of polymer PO6

[0141] The preparation method of polymer PO6 is the same as in Example 1, except that the monomer raw materials are B14 (0.9 eq), B10 (1 eq), and B09 (0.1 eq).

[0142] The yield of polymer PO6 was 62.5%.

[0143] Example 7: Preparation of polymer PO7

[0144] The preparation method of polymer PO7 is the same as in Example 1, except that the monomer raw materials are B10 (0.5 eq), B12 (1 eq), and BO1 (0.5 eq);

[0145] Experimental results: The yield of polymer PO7 was 70.3%.

[0146] Example 8: Preparation of polymer PO8

[0147] The preparation method of polymer P08 is the same as in Example 1, except that the monomer raw materials are B10 (0.75 eq), B09 (1 eq), and B01 (0.25 eq);

[0148] The yield of polymer P08 was 66.3%.

[0149] Example 9: Preparation of polymer PO9

[0150] The preparation method of polymer P09 is the same as in Example 1, except that the monomer raw materials are B10 (0.25 eq), B09 (1 eq), and B18 (0.75 eq);

[0151] The yield of polymer P09 was 71.6%.

[0152] Example 10: Preparation of polymer P10

[0153] The preparation method of polymer P10 is the same as in Example 1, except that the monomer raw materials are B10 (0.25 eq), B09 (0.1 eq), B06 (0.75 eq), and B14 (0.9 eq);

[0154] Experimental results: The yield of polymer P10 was 65.3%.

[0155] Example 11: Preparation of polymer P11

[0156] The preparation method of polymer P11 is the same as in Example 1, except that the monomer raw materials are BO2 (0.25 eq), BO9 (0.5 eq), BO6 (0.75 eq), and B14 (0.5 eq);

[0157] The yield of polymer P11 was 68.6%.

[0158] Example 12: Preparation of polymer P12

[0159] The preparation method of polymer P12 is the same as in Example 1, except that the monomer raw materials are BO2 (0.2 eq), BO9 (0.2 eq), BO5 (0.8 eq), and B14 (0.8 eq);

[0160] The yield of polymer P12 was 59.3%.

[0161] Example 13: Preparation of polymer P13

[0162] The preparation method of polymer P13 is the same as in Example 1, except that the monomer raw materials are B10 (0.25 eq), B09 (0.1 eq), B11 (0.75 eq), and B14 (0.9 eq);

[0163] The yield of polymer P13 was 62.2%.

[0164] Example 14: Preparation of polymer P14

[0165] The preparation method of polymer P14 is the same as in Example 1, except that the monomer raw materials are B07 (0.25 eq), B09 (1 eq), and B15 (0.75 eq);

[0166] The yield of polymer P14 was 60.5%.

[0167] Example 15: Preparation of polymer P15

[0168] The preparation method of polymer P15 is the same as in Example 1, except that the monomer raw materials are B08 (0.25 eq), B14 (1 eq), and B15 (0.75 eq);

[0169] The yield of polymer P15 was 72.5%.

[0170] Example 16: Preparation of polymer P16

[0171] The preparation method of polymer P16 is the same as in Example 1, except that the monomer raw materials are B14 (0.9 eq), B08 (1 eq), and B09 (0.1 eq);

[0172] The yield of polymer P16 was 66.7%.

[0173] Example 17: Preparation of polymer P17

[0174] The preparation method of polymer P17 is the same as in Example 1, except that the monomer raw materials are B16 (0.25 eq), B17 (1 eq), and B14 (0.75 eq);

[0175] The yield of polymer P17 was 59.5%.

[0176] Example 18: Preparation of polymer P18

[0177] The preparation method of polymer P18 is the same as in Example 1, except that the monomer raw materials are B07 (0.25 eq), B09 (0.25 eq), B05 (0.75 eq), and B14 (0.75 eq);

[0178] The yield of polymer P18 was 62.1%.

[0179] Performance testing

[0180] The obtained polymers P1-P18 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.

[0181] 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.

[0182] 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.

[0183] 3) Color test: The neutral and oxidized colors of the polymer film were tested using a spectrophotometer.

[0184] 4) Optical contrast: The maximum optical contrast at a specific wavelength within the visible light region.

[0185] Table 3 shows the CV potential values, transmittance in the neutral state and the oxidized state of Examples 1-18. They all exhibited high transparency in the neutral state and purple, red, brown, green or black in the oxidized state.

[0186] Examples 3 and 13 involved quantitative color measurement (color testing): To accurately assess color characteristic changes during electrochemical conversion, 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 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.

[0187] The oxidation peak potential of Example 3 (PO3) is approximately 1.30V. 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 498 nm is 81.27%. Figure 2 The initial absorption wavelength in the neutral state is approximately 410 nm, with color coordinates L* = 94.81, a* = -2.51, and b* = 8.15, exhibiting as a transparent and colorless thin film.

[0188] In its oxidized state, it exhibits an absorption peak at 499 nm and another, broader peak at approximately 1000 nm. The color coordinates are L* = 45.82, a* = 12.81, b* = 10.47, resulting in a brownish-red color. Figure 3 ).

[0189] The oxidation peak potential of Example 13 (P13) is approximately 1.24V. Figure 4The 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 558 nm is 76.39%. Figure 5 The initial absorption wavelength in the neutral state is approximately 449 nm, with color coordinates L* = 94.37, a* = -8.82, and b* = 19.8, resulting in a slightly yellow hue.

[0190] In its oxidized state, it exhibits an absorption peak at 545 nm and another, broader peak at approximately 1050 nm. Its color coordinates are L* = 47.01, a* = 12.25, and b* = -0.9, resulting in a deep red color. Figure 6 ).

[0191] Table 3 Performance of the polymer films in the examples

[0192]

[0193]

[0194] Table 4 Color Measurement of Polymer Films in Examples

[0195]

[0196] Application examples

[0197] An electrochromic device, comprising

[0198] First electrode: Tin-doped indium oxide (ITO);

[0199] Second electrode: Indium tin oxide (ITO);

[0200] Electrochromic material (any thin film of polymer P01-P18): disposed on the first electrode and located between the first electrode and the second electrode;

[0201] Solid electrolyte: Li+-doped polyethylene oxide (PEO) is placed between the electrochromic material and the second electrode.

[0202] Charge storage layer: V2O5, deposited on the second electrode, positioned between the solid electrolyte and the second electrode.

[0203] The prepared electrochromic devices can be applied to automobile windows, anti-glare rearview mirrors, 3C products, building glass curtain walls, and eyewear.

[0204] 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 at least three of segments A, B, C, D, and E, and contains at least segments A and B. The A and E segments have different chemical structures, and both have the structure shown in general formula (1): The C segment has the structure shown in general formula (2): The chemical structures of fragments B and D are different, and each is independently selected from one of the following general formulas (3), (4), and (5): In the general formula (1), Ar1 and Ar2 are independently represented as substituted or unsubstituted C6-C30 arylene and substituted or unsubstituted C5-C30 heteroarylene, respectively. In the general formula (2), n represents the number of Rb and Ra, and n is selected from 1 to 3; Ra and Rb are independently represented as hydrogen, halogen, substituted or unsubstituted C1-C30 alkyl groups, and adjacent Ra or Rb groups can be linked to form a ring; 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, and substituted or unsubstituted C5-C30 heteroaryl, respectively. In the general formulas (1) and (2), R independently represents 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 Substituted C5-C30 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.

2. The electrochromic material according to claim 1, characterized in that, In the general formulas (1) and (2), R is independently represented as a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C1-C30 alkyl, or a substituted or unsubstituted C3-C30 alkoxyalkyl, respectively.

3. The electrochromic material according to claim 1, characterized in that, The polymer is selected from any one or a combination of the following general formulas: Where n is an integer equal to or greater than 1; w, x, y, z, and u represent mole fractions.

4. The electrochromic material according to claim 3, characterized in that, In general formula (Ⅰ), 0.1≤(w+y):x≤4; in general formula (Ⅱ), 0.1≤w:(x+z)≤4; in general formula (Ⅲ), 0.1≤(w+u):x≤4; In the general formula (Ⅳ), 0.1≤(w+u):(x+z)≤4; In general formula (V), 0.1 ≤ (w+y): (x+z) ≤ 4; in general formula (VI), 0.1 ≤ (w+y): (x+u) ≤ 4.

5. The electrochromic material according to claim 1, characterized in that, The A and E segments are selected from one of the general formulas (A-1), (A-2), or (A-3): n represents 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 C5-C30 heteroaryl. Adjacent R' groups may be linked to form a ring.

6. The electrochromic material according to claim 5, 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.

7. The electrochromic material according to claim 6, characterized in that, In general formula (A-1), R2, R3, R6, and R7 are all hydrogen; in general formula (A-2), R1 and R4 are both hydrogen; in general formula (A-3), R2, R3, and R6 are all hydrogen. The B fragment is of general formula (5) or a combination thereof, and at least one of R3 and R4 in general formula (5) is a substituted or unsubstituted halogen, a substituted or unsubstituted C1-C30 alkyl, a substituted or unsubstituted C1-C30 alkoxy, a substituted or unsubstituted C6-C30 aryl, or a substituted or unsubstituted C5-C30 heteroaryl.

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

9. 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.

10. 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.

11. The electrochromic material according to claim 10, 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.

12. The electrochromic material according to any one of claims 1 to 11, characterized in that, In a neutral state, the absorption initiation wavelength of the electrochromic material is ≤480nm.

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

14. An electrochromic device, characterized in that, include: First electrode; Second electrode: positioned relative to the first electrode; The electrochromic material according to 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.

15. The electrochromic device according to claim 14, 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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