A method for preparing an electrochromic composition and its anodic electrochromic material
By using bis(dimethyldihydrophenazinyl)amine as the anodic color-changing material, combined with a specific formulation and preparation method, the problems of small molecular weight and high cost of materials in existing electrochromic liquids have been solved, achieving rich color gradients and low-cost electrochromic effects, thus improving the performance of the device.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- YANGZHOU JINGCAI OPTOELECTRONICS TECH CO LTD
- Filing Date
- 2026-04-07
- Publication Date
- 2026-06-30
AI Technical Summary
Existing electrochromic liquids have small molecular weights, resulting in insufficient color gradient control and high costs, making it difficult to meet diverse color requirements.
Using bis(dimethyldihydrophenazinyl)amine as the anodic color-changing material, and through a specific formulation and preparation method, combined with cathodic color-changing materials, solvents and stabilizers, an electrochromic composition is formed to achieve rich color gradients and low-cost electrochromic effects.
It achieves richer color gradient control, reduces the cost of using anodic electrochromic materials, improves the response speed and cycle life of devices, and meets the requirements of different color depths.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of electrochromic material manufacturing technology, and more particularly to an electrochromic composition and a method for preparing the anodic electrochromic material thereof. Background Technology
[0002] Electrochromism refers to the phenomenon where a material undergoes a reversible and persistent change in its optical properties under the influence of an applied electric field. Essentially, it is an electrochemical oxidation-reduction process involving the coordinated transport of electrons and ions. Electrochromic devices made from electrochromic materials exhibit reversible changes in transmittance under external voltage, characterized by short response time, high optical contrast, and long cycle life. They have already been applied in fields such as automotive anti-glare rearview mirrors, smart windows, panoramic sunroofs, and displays.
[0003] A Chinese invention patent application with application number CN202511376677.X entitled "A Violet-Anthraquinone Composite Electrochromic Liquid and Its Preparation Method" discloses a violet-anthraquinone composite electrochromic liquid and its preparation method. The formula is as follows: 1.2-2.5 parts of violet salt, 0.8-1.5 parts of anthraquinone derivative, and 8-12 parts of electrolyte (parts are molar parts); the violet salt is ethyl violet tetrafluoroborate, heptyl violet tetrafluoroborate, or octyl violet tetrafluoroborate; the anthraquinone derivative is 1-ethylamino-4-hydroxyanthraquinone or Acid Blue 43; the preparation method is as follows: prepare an electrolyte solution; add violet salt and anthraquinone derivative according to the formula; fully dissolve the electrochromic material to form a homogeneous and transparent initial liquid; and degas the initial liquid to remove dissolved oxygen. The advantages are: after adding viologen salt and anthraquinone derivative to the solution according to the formula ratio, the two color-changing materials dissolve together in the electrolyte. During reduction, the superposition of their absorption spectra can cover the entire visible light region, thereby achieving the black-and-white switching of the electrochromic liquid, resulting in good performance. However, the molecular weight of the material bound to viologen in this electrochromic liquid is still relatively small, and the color gradient control is not rich enough. Therefore, the preparation method of this electrochromic liquid needs further improvement. Summary of the Invention
[0004] The first technical problem to be solved by the present invention is to provide an electrochromic composition that can save on the use of anodic electrochromic materials, reduce costs, and better meet color requirements, in light of the above-mentioned existing technology.
[0005] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows: This electrochromic composition is characterized in that its formulation comprises 0.2-3 parts of cathodic color-changing material, 0.2-3 parts of anodic color-changing material, 89-98.6 parts of solvent, and 1-5 parts of stabilizer, wherein the parts are parts by weight; wherein the anodic color-changing material is bis(dimethyldihydrophenazinyl)amine, and its molecular formula is [insert molecular formula here].
[0006] ,
[0007] Among them, R1 to R 14 They are respectively one of H, CN, OH, NO2, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted heterocyclic groups.
[0008] As an improvement, the cathode color-changing material is preferably one of ethyl viologen perchlorate, ethyl viologen tetrafluoroborate, 1-ethyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, 1-benzyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, ethyl viologen hexafluorophosphate, heptyl viologen perchlorate, heptyl viologen tetrafluoroborate, butyl viologen hexafluorophosphate, 1,1'-diethyl-2,2'-dimethyl-4,4'-bipyridine tetrafluoroborate, butyl viologen tetrafluoroborate, and heptyl viologen hexafluorophosphate.
[0009] As an improvement, the solvent may preferably be one or more of propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, and acetonitrile.
[0010] As an improvement, the stabilizer may preferably be polymethacrylate.
[0011] As an improvement, the specific steps for preparing the electrochromic composition may preferably be as follows:
[0012] 1. Prepare the prepolymer solution. Weigh the stabilizer and solvent according to the formula. Add the stabilizer to the solvent and mix and dissolve at 70-100℃ for 15-60 min. Stir until completely mixed.
[0013] 2. Add cathodic color-changing material: Weigh the cathodic color-changing material according to the formula and add it to the prepolymer solution;
[0014] 3. Add the anodic color-changing material. Weigh the anodic color-changing material according to the formula and add it to the prepolymer solution. Continue stirring until completely dissolved to complete the preparation of the electrochromic composition.
[0015] As a further improvement, after step three is completed, the resulting solution can preferably be degassed to remove oxygen from the solution.
[0016] The second technical problem to be solved by the present invention is to provide a method for preparing an anodic electrochromic material that can save on the use of anodic electrochromic materials, reduce costs, and better meet color requirements, in light of the above-mentioned existing technology.
[0017] The technical solution adopted by the present invention to solve the above-mentioned technical problem is: a method for preparing the anodic electrochromic material of the electrochromic composition, characterized by comprising the following steps:
[0018] A. 680-720g N 4 -(3,4-diaminophenyl)-1,2,4-phenyltriamine and 980-1100 g of catechol were reacted in a container at 151-187 °C for 12 hours.
[0019] B. Cool the reaction mixture to 78–85°C, add 7–10 L of water over 26–35 minutes, allow the mixture to cool to room temperature overnight, and remove the water.
[0020] C. Add 7-10 L of water to the cooled mixture, heat to 68-75°C, cool to 40°C, and remove the water again.
[0021] D. The mixture after cooling is washed again with 7-10 L of water, and the washing temperature is reduced to 60 °C when removing water.
[0022] E. The mixture after further washing is filtered on a filter funnel and air-dried for 26–35 minutes to obtain approximately 1000 g of moist bis(5,10-dihydrophenazin-2-yl)amine containing water.
[0023] The reaction equations for steps A to E are as follows:
[0024]
[0025] F. Add 800 g of moist bis(5,10-dihydrophenazin-2-yl)amine, 3–5 L of acetonitrile, 250–320 g of sodium dithionite, 860–950 g of sodium carbonate, 1–5 L of methyl iodide and 100–200 g of methyltributylammonium chloride to a reaction vessel, and heat the reactants overnight under reflux to approximately 40–70 °C.
[0026] G. Add 8-12 L of water to the reaction vessel and stir at room temperature for 40-60 minutes. Collect the product in the bottle on a filter funnel, wash with 1-5 L of ethanol, and air dry to obtain 1210 g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine.
[0027] The reaction expressions for steps F and G are as follows;
[0028]
[0029] H. Add 1200g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine and 5-10L of toluene to the reaction vessel, heat to 80°C, and filter the solution.
[0030] I. Decant the obtained solution, distill and concentrate to 1.8 L, cool to 90°C, add 1.8 L of ethanol, and cool the mixture to room temperature overnight;
[0031] J. Wash the solid collected on the filter funnel with 1 L of cold ethanol and dry it at 60°C for 90-110 hours to obtain 600 g of orange-red powder product, thus completing the preparation of bis(dimethyldihydrophenazinyl)amine.
[0032] As an improvement, the water used in steps B, C, D, and G can preferably be deionized water.
[0033] As an improvement, in step H, the solution can preferably be filtered by circulating the solution through a filter bag containing 800 g of G-60 charcoal for 2 hours.
[0034] As an improvement, in step J, drying can preferably be carried out in an oven.
[0035] Compared with existing technologies, the advantages of this invention are as follows: The anodic color-changing material uses bis(dimethyldihydrophenazinyl)amine. Bis(dimethyldihydrophenazinyl)amine exhibits two distinct spectral change stages in the two-step oxidation process, thus allowing for richer color gradient control. By changing the concentration, anodic color-changing materials that meet different color depth requirements can be produced, achieving a wider color rendering range. Simultaneously, the violet salt and anodic color-changing material synergistically change color to a grayish-black, representing a novel color change. Furthermore, the strong electron-donating amino groups of bis(dimethyldihydrophenazinyl)amine make the entire molecule more easily oxidized, driving the electrochemical reaction. It features lower pressure and lower energy consumption; the larger molecular weight of bis(dimethyldihydrophenazinyl)amine saves on the use of anodic electrochromic materials, thus reducing costs; the neutral state of bis(dimethyldihydrophenazinyl)amine has a deeper color, which becomes even deeper after oxidation, resulting in a wider range of transmittance variations and improved coloring depth; the oxidation of bis(dimethyldihydrophenazinyl)amine generates relatively stable cationic free radicals (mixed valence states), which are more stable than the divalent cations after complete oxidation of the monomer, thus extending the cycle life of the device; the constructed electrochromic device exhibits excellent response speed performance, reaching millisecond levels, demonstrating superior performance. Detailed Implementation
[0036] The present invention will be further described in detail below with reference to the embodiments.
[0037] The electrochromic composition of the first embodiment comprises a cathodic color-changing material, an anodic color-changing material, a solvent, and a stabilizer. The anodic color-changing material is bis(dimethyldihydrophenazinyl)amine, with the molecular formula [missing information].
[0038] ,
[0039] Among them, R1 to R 14 These are, respectively, one of H, CN, OH, NO2, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, or substituted or unsubstituted heterocyclic groups. Specific alkyl, aryl, amino, and heterocyclic groups are existing technologies and will not be listed individually.
[0040] In this embodiment, the specific proportions of each component in the formula are as follows: 0.2–3g of cathodic color-changing material, 0.2–3g of anodic color-changing material, 89–98.6g of solvent, and 1–5g of stabilizer.
[0041] The cathodic color-changing material is ethyl viologen perchlorate, i.e., EV. + (ClO4 - 2, Ethyl Viologen Difluoroborate, i.e., Ethyl Viologen Difluoroborate, EV + (BF4 - 2,1-Ethyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Et-pCNVio; 1-Benzyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Bn-pCNVio; Ethyl Viologen hexafluorophosphate, i.e., Ethyl Viologen hexafluorophosphate, EV + (PF6 - 2, Heptyl Viologen perchlorate (HV) + (ClO4 - 2), Heptyl Viologen Difluoroborate, also known as HV + (BF4 - 2, Butyl viologen hexafluorophosphate, BV + (PF6 -2,1,1'-Diethyl-2,2'-Dimethyl-4,4'-Bipyridine tetrafluoroborate, butyl viologen tetrafluoroborate, also known as Butyl viologen difluoroborate or BV + (BF4 - 2, Heptyl Viologen hexafluorophosphate, also known as HV + (PF6 - One of )2.
[0042] In this embodiment, ethyl viologen perchlorate is used. The solvent is one or more of propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, and acetonitrile. In this embodiment, propylene carbonate is used. The stabilizer is polymethyl methacrylate.
[0043] The specific steps are as follows:
[0044] 1. Prepare the prepolymer solution. Weigh the stabilizer and solvent according to the formula. The stabilizer content is 1-5 wt%. Add the stabilizer to the solvent and mix and dissolve at 70-100℃ for 15-60 min. Stir until completely mixed.
[0045] 2. Add cathodic color change material. Weigh the cathodic color change material according to the formula. The cathodic color change material content is 5 mmol / L to 50 mol / L. Add the cathodic color change material to the prepolymer solution.
[0046] 3. Add the anodic color-changing material. Weigh the anodic color-changing material according to the formula. The content of the anodic color-changing material is 5 mmol / L to 50 mol / L. Add the anodic color-changing material to the prepolymer solution and continue stirring until completely dissolved. This completes the preparation of the electrochromic composition.
[0047] After step three is completed, the resulting solution is degassed to remove oxygen. In this embodiment, the degassed solution is degassed by introducing nitrogen gas to remove oxygen.
[0048] After removing oxygen, the two pieces of conductive glass coated with indium tin oxide film were cut into pieces with an area of 5×5 cm. 2 The samples were ultrasonically cleaned in anhydrous ethanol, deionized water, and acetone for 0.5 h each, and then dried at 60°C.
[0049] A curing agent is evenly applied around the indium tin oxide glass, leaving an opening. Another piece of ITO glass is then attached to it and baked in an oven to cure, thus obtaining the transparent conductive layer of the EC device.
[0050] An electrochromic reaction mixture solution is encapsulated in a transparent conductive device to fabricate an electrochromic device.
[0051] The method for preparing the anodic electrochromic material of the above-mentioned electrochromic composition includes the following steps:
[0052] A. Add 702 g N to the reaction flask 4 -(3,4-diaminophenyl)-1,2,4-phenyltriamine and 1012 g catechol were reacted at 151–187 °C for 12 hours. The reaction flask was selected according to the capacity of the suitable chemical reaction vessel, which is existing technology, so the specifications and model will not be described in detail.
[0053] B. Cool the reaction mixture to 80°C, add 8 L of water over 30 minutes, allow the mixture to cool to room temperature overnight, and remove the water;
[0054] C. Add 8 L of water to the cooled mixture, heat to 70°C, cool to 40°C, and remove the water again.
[0055] D. The mixture after cooling again is washed with 8 L of water, and the washing temperature is reduced to 60 °C when removing water.
[0056] E. The mixture after further washing is filtered on a filter funnel and air-dried for 30 minutes to obtain approximately 1000 g of moist bis(5,10-dihydrophenazin-2-yl)amine containing water.
[0057] The reaction equations for steps A to E are as follows:
[0058]
[0059] F. Add 800 g of moistened bis(5,10-dihydrophenazin-2-yl)amine, 3.8 L of acetonitrile, 275 g of sodium dithionite, 868 g of sodium carbonate, 1.2 L of methyl iodide and 140 g of methyltributylammonium chloride to the reaction flask, and heat the reaction mixture under reflux overnight to about 40-70°C;
[0060] G. Add 10 L of water to the reaction flask and stir at room temperature for 45 minutes. Collect the product in the flask on a filter funnel, wash with 1 L of ethanol, and air dry to obtain 1210 g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine.
[0061] The reaction expressions for steps F and G are as follows;
[0062]
[0063] H. Add 1200g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine and 6 L of toluene to a 12 L flask, heat to 80°C, and filter the solution.
[0064] I. Decant the obtained solution, distill and concentrate to 1.8 L, cool to 90°C, add 1.8 L of ethanol, and cool the mixture to room temperature overnight;
[0065] J. Wash the solid collected on the filter funnel with 1 L of cold ethanol and dry it in an oven at 60°C for 96 hours to obtain 600 g of orange-red powder product, thus completing the preparation of bis(dimethyldihydrophenazinyl)amine.
[0066] The water used in steps B, C, D, and G is deionized water. In step H, the solution is filtered by circulating it through a filter bag containing 800 g of G-60 charcoal for 2 hours.
[0067] The electrochromic composition of the second embodiment is formulated as follows: it includes a cathodic color-changing material, an anodic color-changing material, a solvent, and a stabilizer. The anodic color-changing material is bis(dimethyldihydrophenazinyl)amine, with the molecular formula:
[0068] ,
[0069] Among them, R1 to R 14 These are, respectively, one of H, CN, OH, NO2, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, or substituted or unsubstituted heterocyclic groups. Specific alkyl, aryl, amino, and heterocyclic groups are existing technologies and will not be listed individually.
[0070] In this embodiment, the specific proportions of each component in the formula are as follows: 0.2–3g of cathodic color-changing material, 0.2–3g of anodic color-changing material, 89–98.6g of solvent, and 1–5g of stabilizer.
[0071] The cathodic color-changing material is ethyl viologen perchlorate, i.e., EV. + (ClO4 - 2, Ethyl Viologen Difluoroborate, i.e., Ethyl Viologen Difluoroborate, EV + (BF4 -2,1-Ethyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Et-pCNVio; 1-Benzyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Bn-pCNVio; Ethyl Viologen hexafluorophosphate, i.e., Ethyl Viologen hexafluorophosphate, EV + (PF6 - 2, Heptyl Viologen perchlorate (HV) + (ClO4 - 2), Heptyl Viologen Difluoroborate, also known as HV + (BF4 - 2, Butyl viologen hexafluorophosphate, BV + (PF6 - 2,1,1'-Diethyl-2,2'-Dimethyl-4,4'-Bipyridine tetrafluoroborate, butyl viologen tetrafluoroborate, also known as Butyl viologen difluoroborate or BV + (BF4 - 2, Heptyl Viologen hexafluorophosphate, also known as HV + (BF6 - One of )2. In this embodiment, ethyl viologen perchlorate is used.
[0072] The solvent is one or more of propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, and acetonitrile. Propylene carbonate is used in this example.
[0073] The stabilizer is polymethyl methacrylate.
[0074] The specific steps are as follows:
[0075] 1. Prepare the prepolymer solution. Weigh the stabilizer and solvent according to the formula. The stabilizer content is 1-5 wt%. Add the stabilizer to the solvent and mix and dissolve at 70-100℃ for 15-60 min. Stir until completely mixed.
[0076] 2. Add cathodic color change material. Weigh the cathodic color change material according to the formula. The cathodic color change material content is 5 mmol / L to 50 mol / L. Add the cathodic color change material to the prepolymer solution.
[0077] 3. Add the anodic color-changing material. Weigh the anodic color-changing material according to the formula. The content of the anodic color-changing material is 5 mmol / L to 50 mol / L. Add the anodic color-changing material to the prepolymer solution and continue stirring until completely dissolved. This completes the preparation of the electrochromic composition.
[0078] After step three is completed, the resulting solution is degassed to remove oxygen. In this embodiment, the degassed solution is degassed by introducing nitrogen gas to remove oxygen.
[0079] After removing oxygen, the two pieces of conductive glass coated with indium tin oxide film were cut into pieces with an area of 5×5 cm. 2 The samples were ultrasonically cleaned in anhydrous ethanol, deionized water, and acetone for 0.5 h each, and then dried at 60°C.
[0080] A curing agent is evenly applied around the indium tin oxide glass, leaving an opening. Another piece of ITO glass is then attached to it and baked in an oven to cure, thus obtaining the transparent conductive layer of the EC device.
[0081] An electrochromic reaction mixture solution is encapsulated in a transparent conductive device to fabricate an electrochromic device.
[0082] The method for preparing the anodic electrochromic material of the above-mentioned electrochromic composition includes the following steps:
[0083] A. Add 680 g of N to the reaction flask 4 -(3,4-diaminophenyl)-1,2,4-phenyltriamine and 980 g catechol were reacted at 151–187 °C for 12 hours. The reaction flask was selected according to its capacity and is a suitable chemical reaction vessel. It is existing technology, so the specifications and model will not be described in detail.
[0084] B. Cool the reaction mixture to 80°C, add 8 L of water over 30 minutes, allow the mixture to cool to room temperature overnight, and remove the water;
[0085] C. Add 8 L of water to the cooled mixture, heat to 70°C, cool to 40°C, and remove the water again.
[0086] D. The mixture after cooling again is washed with 8 L of water, and the washing temperature is reduced to 60 °C when removing water.
[0087] E. The mixture after further washing was filtered on a filter funnel and air-dried for 26 minutes to obtain approximately 1000 g of moist bis(5,10-dihydrophenazin-2-yl)amine containing water.
[0088] The reaction equations for steps A to E are as follows:
[0089]
[0090] F. Add 800 g of moistened bis(5,10-dihydrophenazin-2-yl)amine, 3 L of acetonitrile, 250 g of sodium dithionite, 860 g of sodium carbonate, 1 L of methyl iodide and 100 g of methyl tributylammonium chloride to the reaction flask, and heat the reaction mixture under reflux overnight to about 40-70°C.
[0091] G. Add 10 L of water to the reaction flask and stir at room temperature for 45 minutes. Collect the product in the flask on a filter funnel, wash with 1 L of ethanol, and air dry to obtain 1210 g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine.
[0092] The reaction expressions for steps F and G are as follows;
[0093]
[0094] H. Add 1200g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine and 6 L of toluene to a 12 L flask, heat to 80°C, and filter the solution.
[0095] I. Decant the obtained solution, distill and concentrate to 1.8 L, cool to 90°C, add 1.8 L of ethanol, and cool the mixture to room temperature overnight;
[0096] J. Wash the solid collected on the filter funnel with 1 L of cold ethanol and dry it in an oven at 60°C for 96 hours to obtain 600 g of orange-red powder product, thus completing the preparation of bis(dimethyldihydrophenazinyl)amine.
[0097] The water used in steps B, C, D, and G is deionized water. In step H, the solution is filtered by circulating it through a filter bag containing 800 g of G-60 charcoal for 2 hours.
[0098] The electrochromic composition of the third embodiment is formulated as follows: it includes a cathodic color-changing material, an anodic color-changing material, a solvent, and a stabilizer. The anodic color-changing material is bis(dimethyldihydrophenazinyl)amine, with the molecular formula:
[0099] ,
[0100] Among them, R1 to R 14These are, respectively, one of H, CN, OH, NO2, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, or substituted or unsubstituted heterocyclic groups. Specific alkyl, aryl, amino, and heterocyclic groups are existing technologies and will not be listed individually.
[0101] In this embodiment, the specific proportions of each component in the formula are as follows: 0.2–3g of cathodic color-changing material, 0.2–3g of anodic color-changing material, 89–98.6g of solvent, and 1–5g of stabilizer.
[0102] The cathodic color-changing material is ethyl viologen perchlorate, i.e., EV. + (ClO4 - 2, Ethyl Viologen Difluoroborate, i.e., Ethyl Viologen Difluoroborate, EV + (BF4 - 2,1-Ethyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Et-pCNVio; 1-Benzyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, i.e., Bn-pCNVio; Ethyl Viologen hexafluorophosphate, i.e., Ethyl Viologen hexafluorophosphate, EV + (PF6 - 2, Heptyl Viologen perchlorate (HV) + (ClO4 - 2), Heptyl Viologen Difluoroborate, also known as HV + (BF4 - 2, Butyl viologen hexafluorophosphate, BV + (PF6 - 2,1,1'-Diethyl-2,2'-Dimethyl-4,4'-Bipyridine tetrafluoroborate, butyl viologen tetrafluoroborate, also known as Butyl viologen difluoroborate or BV + (BF4 - 2, Heptyl Viologen hexafluorophosphate, also known as HV + (BF6 - One of )2. In this embodiment, ethyl viologen perchlorate is used.
[0103] The solvent is one or more of propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, and acetonitrile. Propylene carbonate is used in this example.
[0104] The stabilizer is polymethyl methacrylate.
[0105] The specific steps are as follows:
[0106] 1. Prepare the prepolymer solution. Weigh the stabilizer and solvent according to the formula. The stabilizer content is 1-5 wt%. Add the stabilizer to the solvent and mix and dissolve at 70-100℃ for 15-60 min. Stir until completely mixed.
[0107] 2. Add cathodic color change material. Weigh the cathodic color change material according to the formula. The cathodic color change material content is 5 mmol / L to 50 mol / L. Add the cathodic color change material to the prepolymer solution.
[0108] 3. Add the anodic color-changing material. Weigh the anodic color-changing material according to the formula. The content of the anodic color-changing material is 5 mmol / L to 50 mol / L. Add the anodic color-changing material to the prepolymer solution and continue stirring until completely dissolved. This completes the preparation of the electrochromic composition.
[0109] After step three is completed, the resulting solution is degassed to remove oxygen. In this embodiment, the degassed solution is degassed by introducing nitrogen gas to remove oxygen.
[0110] After removing oxygen, the two pieces of conductive glass coated with indium tin oxide film were cut into pieces with an area of 5×5 cm. 2 The samples were ultrasonically cleaned in anhydrous ethanol, deionized water, and acetone for 0.5 h each, and then dried at 60°C.
[0111] A curing agent is evenly applied around the indium tin oxide glass, leaving an opening. Another piece of ITO glass is then attached to it and baked in an oven to cure, thus obtaining the transparent conductive layer of the EC device.
[0112] An electrochromic reaction mixture solution is encapsulated in a transparent conductive device to fabricate an electrochromic device.
[0113] The method for preparing the anodic electrochromic material of the above-mentioned electrochromic composition includes the following steps:
[0114] A. Add 720g N to the reaction flask 4 -(3,4-diaminophenyl)-1,2,4-phenyltriamine and 1100 g catechol were reacted at 151–187 °C for 12 hours. The reaction flask was selected according to the capacity of the suitable chemical reaction vessel, which is existing technology, so the specifications and model will not be described in detail.
[0115] B. Cool the reaction mixture to 85°C, add 8 L of water over 30 minutes, allow the mixture to cool to room temperature overnight, and remove the water;
[0116] C. Add 8 L of water to the cooled mixture, heat to 70°C, cool to 40°C, and remove the water again.
[0117] D. The mixture after cooling again is washed with 8 L of water, and the washing temperature is reduced to 60 °C when removing water.
[0118] E. The mixture after further washing is filtered on a filter funnel and air-dried for 30 minutes to obtain approximately 1000 g of moist bis(5,10-dihydrophenazin-2-yl)amine containing water.
[0119] The reaction equations for steps A to E are as follows:
[0120]
[0121] F. Add 800 g of moistened bis(5,10-dihydrophenazin-2-yl)amine, 5 L of acetonitrile, 320 g of sodium dithionite, 950 g of sodium carbonate, 5 L of methyl iodide and 200 g of methyl tributylammonium chloride to the reaction flask, and heat the reaction mixture under reflux overnight to about 40-70°C.
[0122] G. Add 10 L of water to the reaction flask and stir at room temperature for 45 minutes. Collect the product in the flask on a filter funnel, wash with 1 L of ethanol, and air dry to obtain 1210 g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine.
[0123] The reaction expressions for steps F and G are as follows;
[0124]
[0125] H. Add 1200g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine and 6 L of toluene to a 12 L flask, heat to 80°C, and filter the solution.
[0126] I. Decant the obtained solution, distill and concentrate to 1.8 L, cool to 90°C, add 1.8 L of ethanol, and cool the mixture to room temperature overnight;
[0127] J. Wash the solid collected on the filter funnel with 1 L of cold ethanol and dry it in an oven at 60°C for 96 hours to obtain 600 g of orange-red powder product, thus completing the preparation of bis(dimethyldihydrophenazinyl)amine.
[0128] The water used in steps B, C, D, and G is deionized water. In step H, the solution is filtered by circulating it through a filter bag containing 800 g of G-60 charcoal for 2 hours.
Claims
1. An electrochromic composition, characterized in that: The formulation comprises 0.2-3 parts of cathodic color-changing material, 0.2-3 parts of anodic color-changing material, 89-98.6 parts of solvent, and 1-5 parts of stabilizer, wherein the parts are by weight; wherein the anodic color-changing material is bis(dimethyldihydrophenazinyl)amine, and its molecular formula is [insert molecular formula here]. ， wherein R1to R 14 are each one of H, CN, OH, N02, Br, I, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted amino, substituted or unsubstituted heterocyclyl.
2. The electrochromic composition according to claim 1, characterized in that: The cathode color-changing material is one of the following: ethyl viologen perchlorate, ethyl viologen tetrafluoroborate, 1-ethyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, 1-benzyl-1′-(p-cyanophenyl)-4,4′-bipyridine dibromide, ethyl viologen hexafluorophosphate, heptyl viologen perchlorate, heptyl viologen tetrafluoroborate, butyl viologen hexafluorophosphate, 1,1'-diethyl-2,2'-dimethyl-4,4'-bipyridine tetrafluoroborate, butyl viologen tetrafluoroborate, and heptyl viologen hexafluorophosphate.
3. The electrochromic composition according to claim 1, characterized in that: The solvent is one or more of propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, and acetonitrile.
4. The electrochromic composition according to claim 1, characterized in that: The stabilizer is polymethyl methacrylate.
5. The electrochromic composition according to any one of claims 1 to 4, characterized in that: The specific steps for preparing the electrochromic composition are as follows:
1. Prepare the prepolymer solution. Weigh the stabilizer and solvent according to the formula. Add the stabilizer to the solvent and mix and dissolve at 70-100℃ for 15-60 min. Stir until completely mixed.
2. Add cathodic color-changing material: Weigh the cathodic color-changing material according to the formula and add it to the prepolymer solution; 3. Add the anodic color-changing material. Weigh the anodic color-changing material according to the formula and add it to the prepolymer solution. Continue stirring until completely dissolved to complete the preparation of the electrochromic composition.
6. The electrochromic composition according to claim 5, characterized in that: After step three is completed, the obtained solution is degassed to remove oxygen from the solution.
7. A method for preparing an anodic electrochromic material of an electrochromic composition, characterized in that: Includes the following steps, A. 680-720g N 4 -(3,4-diaminophenyl)-1,2,4-phenyltriamine and 980-1100 g of catechol were reacted in a container at 151-187 °C for 12 hours. B. Cool the reaction mixture to 78–85°C, add 7–10 L of water over 26–35 minutes, allow the mixture to cool to room temperature overnight, and remove the water. C. Add 7-10 L of water to the cooled mixture, heat to 68-75°C, cool to 40°C, and remove the water again. D. The mixture after cooling is washed again with 7-10 L of water, and the washing temperature is reduced to 60 °C when removing water. E. The further washed mixture is filtered through a filter funnel and air-dried for 26–35 minutes to obtain approximately 1000 g of moist bis(5,10-dihydrophenazin-2-yl)amine containing water; the reaction formulas for steps A to E are as follows: F. Add 800 g of moist bis(5,10-dihydrophenazin-2-yl)amine, 3–5 L of acetonitrile, 250–320 g of sodium dithionite, 860–950 g of sodium carbonate, 1–5 L of methyl iodide and 100–200 g of methyltributylammonium chloride to a reaction vessel, and heat the reactants overnight under reflux to approximately 40–70 °C. G. Add 8–12 L of water to the reaction vessel and stir at room temperature for 40–60 minutes. Collect the product in the bottle on a filter funnel, wash with 1–5 L of ethanol, and air dry to obtain 1210 g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine; The reaction formulas for steps F and G are as follows; H. Add 1200g of crude N,N-bis(5,10-dimethyl-5,10-dihydrophenazin-2-yl)amine and 5-10L of toluene to the reaction vessel, heat to 80°C, and filter the solution. I. Decant the obtained solution, distill and concentrate to 1.8 L, cool to 90°C, add 1.8 L of ethanol, and cool the mixture to room temperature overnight; J. Wash the solid collected on the filter funnel with 1 L of cold ethanol and dry it at 60°C for 90-110 hours to obtain 600 g of orange-red powder product, thus completing the preparation of bis(dimethyldihydrophenazinyl)amine.
8. The preparation method according to claim 7, characterized in that: The water used in steps B, C, D, and G is deionized water.
9. The preparation method according to claim 7, characterized in that: In step H, the solution is filtered by circulating it through a filter bag containing 800 g of G-60 charcoal for 2 hours.
10. The preparation method according to claim 7, characterized in that: In step J, drying is performed in an oven.