A high-performance solid-state electrochromic polymer film and a preparation method thereof

Abstract

This invention belongs to the field of electrochromic polymer composite materials technology, specifically relating to a method for preparing a high-performance solid electrochromic polymer film using electrospinning. Electrochromic glass can be widely used in many fields such as construction, office and conference rooms, automobiles, and aerospace. How to prepare impact-resistant electrochromic safety laminated glass is one of the core technologies in this field. In this invention, a solid electrochromic polymer film is prepared using electrospinning technology. This material possesses excellent mechanical properties and high ionic conductivity. More importantly, the liquid content of this solid electrochromic polymer film is extremely low, greatly reducing the difficulty of encapsulation and avoiding the problems of liquid electrolyte leakage polluting the environment and difficult encapsulation. This allows for large-scale application in the actual production of electrochromic glass.

Description

Technical Field

[0001] This invention relates to the field of electrochromic materials, specifically to a high-performance solid electrochromic polymer film and its preparation method. Background Technology

[0002] Electrochromic materials exhibit reversible changes in optical properties under external voltage. Based on these optical characteristics, electrochromic materials and devices have been widely used in smart windows, goggles, and anti-glare rearview mirrors. With the development of the times and the advancement of technology, the functionality of electrochromic technology has been continuously enhanced, and a series of new electrochromic materials and devices, such as flexible, dual-band, and mid-to-far-infrared materials, have emerged, expanding their applications in smart clothing, aerospace, and multi-color displays. However, most existing studies utilize liquid or gel electrolytes to assemble electrochromic devices, leading to problems such as narrow electrochemical windows, easy decomposition under high voltage, difficult encapsulation, flammability, and easy leakage. In contrast, all-solid-state polymer electrolytes contain no organic solvents, possess good mechanical properties, high electrochemical and thermal stability, and have a simple preparation process, showing great development potential. However, the low ionic conductivity of all-solid-state electrolytes limits their rapid development. Therefore, developing all-solid-state electrolytes with high permeability, flexibility, and ionic conductivity for application in electrochromic devices is an urgent problem to be solved.

[0003] In practical applications, the fabrication of impact-resistant electrochromic safety glass has become a core technology. Developing glass with good impact resistance, light transmittance, and rapid response speed is crucial for its further applications. Patent CN 107422564 A describes the preparation of a PVB porous electrolyte film via electrospinning, followed by immersion in a lithium perchlorate-propylene carbonate solution to improve its ionic conductivity and mechanical properties. Patent CN 111474792 A modifies PMMA with propylene carbonate to enhance the ionic conductivity of the electrolyte film. While the electrolyte films prepared using these techniques possess electrochromic properties, laminated glass made from them cannot withstand strong external impacts and lacks safety characteristics. Improving the impact resistance of electrochromic polymer films and providing better safety is a pressing technical challenge for the industry. Summary of the Invention

[0004] To address the above technical problems, this invention provides a solid electrochromic polymer film that not only has high ionic conductivity but also excellent mechanical properties and impact resistance. Furthermore, it aims to provide a method for producing solid electrochromic polymer films that is simple to manufacture, has easily controllable conditions, and low production costs.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] This invention provides a method for preparing a solid electrochromic polymer film, comprising: preparing a spinning solution, a spinning film, and an electrolyte solution respectively, then immersing the spinning film in the electrolyte solution, and drying it to obtain a solid electrochromic polymer film.

[0007] Preferably, the solid electrochromic polymer film spinning process is as follows:

[0008] Flow rate: 0.3–3 ml / h;

[0009] Voltage 3~50kV;

[0010] Spinning time: 0.5–24 hours;

[0011] The distance between the needle and the receiver is 3-50cm;

[0012] The ambient temperature for spinning is -10 to 85℃.

[0013] Ambient humidity: 2–90%.

[0014] This invention also provides a method for preparing a solid electrochromic polymer film, comprising the following steps:

[0015] (1) Add a certain amount of solvent A and solvent B to a container, then add polymer A and polymer B, heat and stir at a temperature above 60°C for 9 to 24 hours to fully dissolve, add a certain amount of plasticizer, antioxidant and ultraviolet absorber, continue stirring at a temperature above 60°C for 3 to 6 hours, then sonicate for 10 to 30 minutes to disperse evenly, and obtain the required spinning solution; the proportions are as follows: polymer A: 100 parts (by weight); polymer B: 0 to 80 parts; solvent A: 10 to 300 parts; solvent B: 10 to 500 parts; plasticizer: 5 to 50 parts; antioxidant: 0 to 10 parts; ultraviolet absorber: 0 to 10 parts; other additives: 0 to 15 parts; electrolyte: 20 to 500 parts;

[0016] (2) Using the above spinning solution, a spun membrane is prepared by electrospinning.

[0017] (3) Prepare an electrolyte solution of 0.1-3 mol / L, immerse the prepared spinning membrane in the electrolyte solution for 30 min-24 h, and then place the immersed membrane in an oven at 55°C for 2-6 h to obtain the electrolyte membrane.

[0018] Preferably, solvent A in step (1) is one or more of anhydrous ethanol, methanol, distilled water, ethyl acetate, thionyl chloride, acetone, toluene, chloroform, formic acid, acetic acid, tetrahydrofuran, methyl ether, and diethyl ether.

[0019] Preferably, the solvent B in step (1) is one or more of N, N-dimethylformamide, ethanol, xylene, toluene, n-butyl acetate, ethyl acetate, isopropanol, phenolic resin, epoxy resin, alkyd, resin and melamine resin, N-methylpyrrolidone and pyridine.

[0020] Preferably, the polymer A in step (1) is one or more of polyurethane, methyl methacrylate, ethylene oxide, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl chloride, and polytetrafluoroethylene.

[0021] Preferably, the polymer B in step (1) is one or more of polyvinyl butyral, polyaniline, polypyrrole, polyacetylene, poly(3,4-ethylenedioxythiophene), polyurethane, and brominated polyphenylene ether.

[0022] Preferably, the plasticizer in step (1) is one or more of the following: triethylene glycol diisooctyl ester, diisooctyl adipate, propylene carbonate, ethyl acetate, dioctyl sebacate, dioctyl phthalate, di-n-hexyl adipate, diisononyl phthalate, and dibutyl sebacate.

[0023] Preferably, the antioxidant in step (1) is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, and tris(2,4-di-tert-butylphenyl) phosphite.

[0024] Preferably, the ultraviolet absorber in step (1) is one or more of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(5-chloro-2H-benzotriazole-2-yl)-4,6-bis(1,1-dimethylethyl)phenol and hexamethylphosphoric acid triamine.

[0025] Preferably, the dispersant in step (1) is one or more of the following: fatty acid polyethylene glycol ester, sodium dodecyl sulfate, sodium tripolyphosphate, and polyethylene glycol 200.

[0026] Preferably, the heat stabilizer in step (1) is one or more of tribasic lead sulfate, dibasic lead phosphite, and dibasic lead stearate.

[0027] Preferably, the light-shielding agent in step (1) is one or more of carbon black, titanium dioxide, and zinc oxide.

[0028] Preferably, the defoamer in step (1) is one or more of tributyl phosphate, GPE10, trioctyl phosphate, and ethylene glycol monostearate.

[0029] Preferably, the conductive agent in step (1) is one or more of SP-Li, conductive graphite, and Ketjen black.

[0030] Preferably, the matting agent in step (1) is one or more of DA-60, titanium dioxide, and ultrafine silica.

[0031] Preferably, the toughening agent in step (1) is one or more of 302 polyester, polysulfide rubber, and chloroprene rubber.

[0032] Preferably, the electrolyte in step (3) is one or more of lithium perchlorate, sodium chloride, lithium chloride, potassium chloride, lithium borate, lithium phosphate, lithium hexafluorophosphate, lithium hexafluoroarsenate, and lithium tetrafluoroborate.

[0033] 1. The solid electrochromic polymer membrane prepared by electrospinning technology in this invention has a porous three-dimensional structure, which is beneficial for the adsorption of liquid electrolytes. Its porous structure facilitates ion transport, increasing the "complexation-decomplexation" rate of lithium ions on the polymer segments, thereby obtaining a polymer system with high ionic conductivity and excellent mechanical properties. The prepared solid electrochromic polymer membrane not only has high conductivity but also improves the impact resistance and tensile mechanical properties of the electrolyte membrane, thus greatly enhancing the safety of the solid electrochromic polymer membrane.

[0034] 2. The solid electrochromic polymer membrane prepared in this invention has a simple process, low cost, and is suitable for large-area preparation and industrialization. The solid electrochromic polymer membrane prepared by this method is easy to encapsulate, and can be encapsulated by hot pressing, avoiding the disadvantages of easy leakage of liquid electrolytes and poor mechanical properties of gel electrolyte membranes.

[0035] Compared with existing technologies, the solid electrochromic polymer membrane prepared in this invention not only possesses high ionic conductivity but also excellent mechanical properties and impact resistance. It also solves the problems of easy leakage in liquid electrolytes and poor mechanical properties in gel electrolyte membranes. The ionic conductivity of the electrolyte membrane can reach 1.46 × 10⁻⁶. -5 S / cm, its impact resistance is stable.

[0036] It can withstand the impact of a falling ball from a height of 130cm, enhancing the safety of laminated glass. Its tensile strength reaches 6.03MPa, exceeding the ionic conductivity and mechanical properties of commercially available solid porous electrochromic electrolyte membranes. Therefore, the solid electrochromic polymer membrane of this invention has broad application prospects.

[0037] Implementation

[0038] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0039] This invention provides a method for preparing a solid electrochromic polymer film, comprising: preparing a spinning solution, a spinning film, and an electrolyte solution respectively, then immersing the spinning film in the electrolyte solution, and drying it to obtain a solid electrochromic polymer film.

[0040] In this invention, the solid electrochromic polymer film spinning process is as follows:

[0041] Flow rate: 0.3–3 ml / h;

[0042] Voltage 3~50kV;

[0043] Spinning time: 0.5–24 hours;

[0044] The distance between the needle and the receiver is 3-50cm;

[0045] The ambient temperature for spinning is -10 to 85℃.

[0046] Ambient humidity: 2–90%.

[0047] In this invention, the preferred mass fraction of polymer A is 100 parts (by weight); the preferred mass fraction of polymer B is 0-80 parts, most preferably 20-60 parts; the preferred mass fraction of solvent A is 10-300 parts, most preferably 80-200 parts; the preferred mass fraction of solvent B is 10-500 parts, most preferably 100-300 parts; the preferred mass fraction of plasticizer is 5-50 parts, most preferably 20-35 parts; the preferred mass fraction of antioxidant is 0-10 parts, most preferably 0.5-5 parts; the preferred mass fraction of ultraviolet absorber is 0-10 parts, most preferably 0.5-5 parts; the preferred mass fraction of other additives is 0-15 parts, most preferably 5-10 parts; and the preferred mass fraction of electrolyte is 20-500 parts, most preferably 100-350 parts.

[0048] All raw materials used in the following embodiments of the present invention are commercially available products. Attached Figure Description

[0049] Figure 1 Scanning electron microscope image of the solid electrolyte membrane prepared in Example 1.

[0050] Figure 2 Impedance diagram of the solid electrolyte membrane prepared in Example 1.

[0051] Figure 3 The transmittance is the solid electrolyte membrane prepared in Example 1.

[0052] Figure 4 The stress-strain curve of the solid electrolyte membrane prepared in Example 1 is shown.

[0053] Figure 5 This is a schematic diagram of an impact resistance test of a solid polymer film. Detailed Implementation

[0054] To further illustrate the present invention, the following detailed description of a method for preparing a solid electrochromic polymer film provided by the present invention is provided in conjunction with embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0055] Test method:

[0056] Mechanical property testing: Samples were prepared and tested according to the national standard GB / T 1040.3-2006 Determination of tensile properties of plastics - Part 3: Test conditions for thin plastics and sheets.

[0057] Transmittance test: Samples were prepared and tested according to the national standard GB / T 2410-2008 Determination of transmittance and haze of transparent plastics.

[0058] Impact resistance test: The prepared laminated glass samples were subjected to impact resistance testing at room temperature using a falling ball impact tester. Figure 5 As shown: The test specimen is a 4 cm × 4 cm square flat test piece. A 20 g steel ball is used to impact the laminated glass specimen from different heights via free fall. The evaluation method is as follows: if the glass cracks after impact, the result is recorded as unqualified, i.e., "×"; if the glass does not crack after impact, the result is recorded as qualified, i.e., "√".

[0059] Ionic conductivity testing: The AC impedance of the polymer film was tested using an electrochemical workstation with an amplitude of 100 mV and a frequency scan range of 0.1 Hz to 10 Hz. 5 Hz. The measured AC impedance spectral data are used to perform data simulation to obtain the bulk resistance of the sample. From the bulk resistance, according to the formula... (Where d, R, and S represent the thickness, area, and bulk resistance of the electrolyte membrane, respectively), the ionic conductivity is calculated. The ionic conductivity of the thin films prepared in the following examples was tested using this method.

[0060] (1) Add 0.1g chloroform, 5g DMF, 1.0g polypyrrole to a reaction vessel containing 0.8g polymethyl methacrylate. Heat and stir at 80°C for 12 hours until fully dissolved. Then add 0.5g propylene carbonate, 0.1g 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 0.1g sodium dodecyl sulfate and 0.1g SP-Li. Continue stirring at 60°C for 12 hours. Then sonicate for 30 minutes to disperse evenly and obtain the desired spinning solution.

[0061] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 0.8 ml / h, voltage of 15 kV, receiving distance of 15 cm, spinning temperature of 20°C, spinning humidity of 30%, and spinning time of 2 hours.

[0062] (3) Prepare a 3 mol / L sodium chloride solution, immerse the spun membrane prepared above in the sodium chloride solution for 2 h, and then place the immersed membrane in an oven at 55 °C for 3 h to obtain an electrolyte membrane.

[0063] (1) Add 3g ethyl acetate, 0.1g DMF and 1.0g polyvinyl butyral to a reaction vessel, heat and stir at 80°C for 12 hours until fully dissolved, then add 0.05g methyl ethyl carbonate, 0.1g triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 0.005g 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 0.05g trioctyl phosphate and 0.05g ultrafine silica, continue stirring at 60°C for 12 hours, and then sonicate for 25 minutes to disperse evenly to obtain the desired spinning solution;

[0064] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55℃ for 2 hours to obtain the desired sample. The preparation conditions were: flow rate of 0.3 ml / h, voltage of 3 kV, receiving distance of 3 cm, spinning temperature of -10℃, spinning humidity of 10%, and spinning time of 0.5 h.

[0065] (3) Prepare a 0.1 mol / L lithium phosphate solution, immerse the prepared spinning membrane in the lithium phosphate solution for 24 h, and then place the immersed membrane in an oven at 55 °C for 3 h to obtain an electrolyte membrane.

[0066] (1) Add 0.8g anhydrous ethanol, 3g DMF, 1.0g ethylene oxide and 0.2g polyvinylidene fluoride to a reaction vessel, heat and stir at 60°C for 8 hours to fully dissolve, then add 0.2g triethylene glycol diisooctanoate, 0.005g pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.06g ethylene glycol monostearate and 0.05g DA-60, continue stirring at 80°C for 24 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0067] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 2 hours to obtain the desired sample. The preparation conditions were: flow rate of 3 ml / h, voltage of 50 kV, receiving distance of 50 cm, spinning temperature of 85°C, spinning humidity of 90%, and spinning time of 24 hours.

[0068] (3) Prepare a 1 mol / L lithium perchlorate solution, immerse the prepared spinning membrane in the lithium perchlorate solution for 12 h, and then place the immersed membrane in an oven at 55 °C for 3 h to obtain an electrolyte membrane.

[0069] (1) Add 2.5g of dimethyl ether, 3.5g of DMF, 1.0g of polyvinyl butyral and 0.7g of polyvinylidene fluoride to a reaction vessel, heat and stir at 80°C for 24 hours until fully dissolved, then add 0.008g of 1,2-bis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 0.008g of 2-hydroxy-4-n-octyloxybenzophenone and 0.08g of ethylene glycol monostearate, continue stirring at 80°C for 8 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0070] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 1 ml / h, voltage of 22 kV, receiving distance of 20 cm, spinning temperature of 60°C, spinning humidity of 2%, and spinning time of 15 hours.

[0071] (3) Prepare a 2.5 mol / L lithium hexafluorophosphate solution, immerse the prepared spinning membrane in the lithium hexafluorophosphate solution for 15 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0072] (1) Add 0.8g tetrahydrofuran, 3g sulfoxide, 1.0g polyurethane and 0.2g polytetrafluoroethylene to a reaction vessel, heat and stir at 80°C for 12 hours until fully dissolved, then add 0.2g diisooctyl adipate, 0.005g triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate and 0.05g 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-di(1,1-dimethylethyl)phenol, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0073] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 1.5 ml / h, voltage of 30 kV, receiving distance of 30 cm, spinning temperature of 30°C, spinning humidity of 30%, and spinning time of 10 hours.

[0074] (3) Prepare a 1.5 mol / L lithium chloride solution, immerse the prepared spinning membrane in the lithium chloride solution for 18 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0075] (1) Add 1g isopropanol, 2g DMF, 1.0g polyaniline and 0.6g polymethyl methacrylate to a reaction vessel, heat and stir at 60°C for 12 hours until fully dissolved, then add 0.35g diisononyl phthalate, 0.05g tris(2,4-di-tert-butylphenyl) phosphite, 0.005g 2-hydroxy-4-n-octyloxybenzophenone, 0.15g conductive graphite and 0.15g titanium dioxide, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0076] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 0.5 ml / h, voltage of 18 kV, receiving distance of 15 cm, spinning temperature of 20°C, spinning humidity of 15%, and spinning time of 5 hours.

[0077] (3) Prepare a 0.5 mol / L lithium borate solution, immerse the prepared spinning membrane in the lithium borate solution for 6 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0078] (1) Add 2.8g acetone, 4.2g DMF, 1.0g polyvinyl butyral and 0.33g polymethyl methacrylate to a reaction vessel, heat and stir at 60°C for 24 hours until fully dissolved, then add 0.3g triethylene glycol diisooctanoate, 0.045g 4,4'-thiobis(6-tert-butyl-3-methylphenol), 0.035g 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 0.05g chloroprene rubber and 0.05g tributyl phosphate, continue stirring at 80°C for 12 hours, then sonicate for 20 minutes to disperse evenly, to obtain the desired spinning solution;

[0079] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 1 ml / h, voltage of 17.5 kV, receiving distance of 17 cm, spinning temperature of 22°C, spinning humidity of 15%, and spinning time of 3 hours.

[0080] (3) Prepare a 1.5 mol / L lithium perchlorate solution, immerse the prepared spinning membrane in the lithium perchlorate solution for 12 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0081] (1) Add 1.2g anhydrous ethanol, 2.8g DMF, 1.0g polypyrrole and 0.5g polyvinylidene fluoride to a reaction vessel, heat and stir at 60°C for 8 hours to fully dissolve, then add 0.28g ethyl acetate, 0.035g triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 0.005g 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-di(1,1-dimethylethyl)phenol and 0.1g ethylene glycol monostearate acid, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0082] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 2.5 ml / h, voltage of 30 kV, receiving distance of 25 cm, spinning temperature of 5°C, spinning humidity of 10%, and spinning time of 6 hours.

[0083] (3) Prepare a 0.8 mol / L lithium phosphate solution, immerse the prepared spinning membrane in the lithium phosphate solution for 12 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0084] (1) Add 1.8g thionyl chloride, 2.2g DMF, 1.0g poly(3,4-ethylenedioxythiophene) and 0.4g ethylene oxide to a reaction vessel, heat and stir at 90°C for 6 hours until fully dissolved, then add 0.3g dioctyl phthalate, 0.025g β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate n-octadecyl alcohol, 0.025g hexamethylphosphoric acid triamine, 0.04g ethylene glycol monostearate, 0.05g dibasic lead phosphite and 0.03g carbon black, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0085] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 1.3 ml / h, voltage of 18 kV, receiving distance of 13 cm, spinning temperature of 15°C, spinning humidity of 25%, and spinning time of 15 hours.

[0086] (3) Prepare a 2 mol / L lithium hexafluorophosphate solution, immerse the prepared spinning membrane in the lithium hexafluorophosphate solution for 8 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0087] (1) Add 1.5g of diethyl ether, 2.5g of DMF, 1.0g of polyacetylene and 0.55g of polymethyl methacrylate to a reaction vessel, heat and stir at 80°C for 36 hours until fully dissolved, then add 0.28g of diisooctyl adipate, 0.05g of 4,4'-thiobis(6-tert-butyl-3-methylphenol), 0.03g of 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)phenol and 0.1g of GPE10, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0088] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 1 ml / h, voltage of 18 kV, receiving distance of 18 cm, spinning temperature of 23°C, spinning humidity of 15%, and spinning time of 2 hours.

[0089] (3) Prepare a 1.8 mol / L lithium hexafluoroarsenate solution, immerse the prepared spinning membrane in the lithium hexafluoroarsenate solution for 12 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0090] (1) Add 1.7g toluene, 2.3g DMF, 1.0g polyacetylene and 0.7g polyvinylidene fluoride to a reaction vessel, heat and stir at 60°C for 24 hours until fully dissolved, then add 0.3g dibutyl sebacate, 0.01g triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 0.01g hexamethylphosphoric triamine and 0.05g GPE10, continue stirring at 60°C for 12 hours, and then sonicate for 30 minutes to disperse evenly to obtain the desired spinning solution;

[0091] (2) Using the above spinning solution, a fiber spinning membrane was prepared by electrospinning device. The spinning membrane was placed in an oven at 55°C for 6 hours to obtain the desired sample. The preparation conditions were: flow rate of 0.6 ml / h, voltage of 17.5 kV, receiving distance of 17 cm, spinning temperature of 20°C, spinning humidity of 20%, and spinning time of 3 hours.

[0092] (3) Prepare a 2.2 mol / L lithium tetrafluoroborate solution, immerse the prepared spinning membrane in the lithium tetrafluoroborate solution for 12 h, and then place the immersed membrane in an oven at 55 °C for 6 h to obtain an electrolyte membrane.

[0093] Currently, among the reported patents, patent CN 107422564 A describes a method for preparing porous quasi-solid-state electrochromic PVB electrolyte membranes by electrospinning. The method is characterized by dissolving polyvinyl butyral in ethanol to form a spinning solution for spinning, and then immersing the resulting spun membrane in a lithium salt propylene carbonate solution to prepare an electrolyte membrane.

[0094] Currently, among the reported patents, patent CN 111474792 A describes a method for preparing porous electrochromic films using electrospinning. The method is characterized by dissolving TPA-OMe-PA and silver nanowires (AgNWs) in N,N-dimethylacetamide (DMAc) and then spinning them to obtain an electrolyte film.

[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

[0096] Table 1. Ionic conductivity and tensile strength test results of the examples and comparative examples.

[0097] sample Electrical conductivity (S / cm) Light transmittance (T%) GB / T 2410-2008 Tensile strength (MPa) GB / T 040.3-2006 Example 1 <![CDATA[5.95×10 -6 ]]> 74 3.65 Example 2 <![CDATA[7.89×10 -5 ]]> 79 5.95 Example 3 <![CDATA[6.73×10 -5 ]]> 75 5.34 Example 4 <![CDATA[2.39×10 -6 ]]> 80 5.03 Example 5 <![CDATA[4.35×10 -5 ]]> 76 3.67 Example 6 <![CDATA[6.45×10 -5 ]]> 75 3.85 Example 7 <![CDATA[1.45×10 -5 ]]> 85 6.03 Example 8 <![CDATA[7..83×10 -5 ]]> 79 4.17 Example 9 <![CDATA[8.56×10 -5 ]]> 77 4.25 Example 10 <![CDATA[8.73×10 -5 ]]> 81 3.54 Example 11 <![CDATA[7.98×10 -5 ]]> 82 4.23 Comparative Example 1 <![CDATA[9.21×10 -4 ]]> 79 0.35 Comparative Example 2 <![CDATA[3.71×10 -5 ]]> 86 ×

[0098] Table 2. Impact resistance test results at different heights for the examples and comparative examples.

[0099] 80cm 90 cm 100 cm 110cm 120cm 130cm 140 cm Example 1 √ √ × Example 2 √ √ √ × Example 3 √ √ √ √ × Example 4 √ √ × Example 5 × Example 6 √ × Example 7 √ √ √ √ √ √ × Example 8 √ √ √ √ × Example 9 √ × Example 10 √ √ √ × Example 11 √ √ × Comparative Example 1 none Comparative Example 2 none

Claims

1. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 1 part by weight of chloroform, 50 parts by weight of DMF, 10 parts by weight of polypyrrole to a reaction vessel containing 8 parts by weight of polymethyl methacrylate, heat and stir until fully dissolved, then add 5 parts by weight of propylene carbonate, 1 part by weight of 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-benzotriazole, 1 part by weight of sodium dodecyl sulfate and 1 part by weight of SP-Li, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 3 mol / L sodium chloride solution, immerse the prepared spinning membrane in the sodium chloride solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

2. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 30 parts by weight of ethyl acetate, 1 part by weight of DMF, and 10 parts by weight of polyvinyl butyral to a reaction vessel. Heat and stir until fully dissolved. Then add 0.5 parts by weight of methyl ethyl carbonate, 1 part by weight of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 0.05 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 0.5 parts by weight of trioctyl phosphate, and 0.5 parts by weight of ultrafine silica. Continue stirring and then sonicate to disperse evenly to obtain the desired spinning solution. (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 0.1 mol / L lithium phosphate solution, immerse the prepared spinning membrane in the lithium phosphate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

3. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 8 parts by weight of anhydrous ethanol, 30 parts by weight of DMF, 10 parts by weight of ethylene oxide and 2 parts by weight of polyvinylidene fluoride to a reaction vessel, heat and stir until fully dissolved, then add 2 parts by weight of triethylene glycol diisooctanoate, 0.05 parts by weight of pentaerythritol tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 0.6 parts by weight of ethylene glycol monostearate and 0.5 parts by weight of DA-60, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution. (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 1 mol / L lithium perchlorate solution, immerse the prepared spinning membrane in the lithium perchlorate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

4. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 25 parts by weight of methyl ether, 35 parts by weight of DMF, 10 parts by weight of polyvinyl butyral and 7 parts by weight of polyvinylidene fluoride into a reaction vessel, heat and stir until fully dissolved, then add 0.08 parts by weight of 1,2-bis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 0.08 parts by weight of 2-hydroxy-4-n-octyloxybenzophenone and 0.8 parts by weight of ethylene glycol monostearate, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 2.5 mol / L lithium hexafluorophosphate solution, immerse the spun membrane prepared above in the lithium hexafluorophosphate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

5. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 8 parts by weight of tetrahydrofuran, 30 parts by weight of sulfonium chloride, 10 parts by weight of polyurethane and 2 parts by weight of polytetrafluoroethylene into a reaction vessel, heat and stir until fully dissolved, then add 2 parts by weight of diisooctyl adipic acid, 0.05 parts by weight of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionic acid and 0.5 parts by weight of 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)phenol, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution. (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 1.5 mol / L lithium chloride solution, immerse the prepared spinning membrane in the lithium chloride solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

6. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 10 parts by weight of isopropanol, 20 parts by weight of DMF, 10 parts by weight of polyaniline and 6 parts by weight of polymethyl methacrylate to a reaction vessel, heat and stir until fully dissolved, then add 3.5 parts by weight of diisononyl phthalate, 0.5 parts by weight of tris(2,4-di-tert-butylphenyl) phosphite, 0.05 parts by weight of 2-hydroxy-4-1-octyloxybenzophenone, 1.5 parts by weight of conductive graphite and 1.5 parts by weight of titanium dioxide, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 0.5 mol / L lithium borate solution, immerse the spun membrane prepared above in the lithium borate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

7. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 28 parts by weight of acetone, 42 parts by weight of DMF, 10 parts by weight of polyvinyl butyral and 3.3 parts by weight of polymethyl methacrylate to a reaction vessel, heat and stir until fully dissolved, then add 3 parts by weight of triethylene glycol diisooctanoate, 0.45 parts by weight of 4,4'-thiobis(6-tert-butyl-3-methylphenol) and 0.35 parts by weight of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole. Mix 0.5 parts by weight of chloroprene rubber and 0.5 parts by weight of tributyl phosphate, continue stirring, and then sonicate to disperse them evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 1.5 mol / L lithium perchlorate solution, and immerse the prepared spinning membrane in the lithium perchlorate solution. After 12 hours, the soaked membrane is placed in an oven to evaporate the solvent, thus obtaining an electrolyte membrane.

8. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 12 parts by weight of anhydrous ethanol, 28 parts by weight of DMF, 10 parts by weight of polypyrrole and 5 parts by weight of polyvinylidene fluoride to a reaction vessel, heat and stir until fully dissolved, then add 2.8 parts by weight of ethyl acetate and 0.35 parts by weight of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. 0.05 parts by weight of 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-di(1,1-dimethylethyl)phenol and 1 part by weight of ethylene glycol monostearate acid were stirred and then ultrasonically dispersed to obtain the desired spinning solution. (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 0.8 mol / L lithium phosphate solution, immerse the prepared spinning membrane in the lithium phosphate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

9. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 18 parts by weight of sulfoxide, 22 parts by weight of DMF, 10 parts by weight of poly(3,4-ethylenedioxythiophene) and 4 parts by weight of ethylene oxide to a reaction vessel, heat and stir until fully dissolved, then add 3 parts by weight of dioctyl phthalate, 0.25 parts by weight of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate E octadecyl alcohol ester, 0.25 parts by weight of hexamethylphosphoric acid triamine, 0.4 parts by weight of ethylene glycol monostearate, 0.5 parts by weight of dibasic lead phosphite and 0.3 parts by weight of carbon black, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 2 mol / L lithium hexafluorophosphate solution, immerse the prepared spinning membrane in the lithium hexafluorophosphate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

10. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 15 parts by weight of diethyl ether, 25 parts by weight of DMF, 10 parts by weight of polyacetylene and 5.5 parts by weight of polymethyl methacrylate to a reaction vessel, heat and stir until fully dissolved, then add 2.8 parts by weight of diisooctyl adipate, 0.5 parts by weight of 4,4'-thiobis(6-tert-butyl-3-methylphenol), 0.3 parts by weight of 2-(5-chloro-2H-benzotriazol-2-yl)-4,6-bis(1,1-dimethylethyl)phenol and 1 part by weight of GPE10, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution; (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 1.8 mol / L lithium hexafluoroarsenate solution, immerse the prepared spinning membrane in the lithium hexafluoroarsenate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

11. A method for preparing a high-performance solid-state electrochromic polymer film, characterized in that, The method includes the following steps: (1) Add 17 parts by weight of toluene, 23 parts by weight of DMF, 10 parts by weight of polyacetylene and 7 parts by weight of polyvinylidene fluoride into a reaction vessel, heat and stir until fully dissolved, then add 3 parts by weight of dibutyl sebacate, 0.1 parts by weight of triethylene glycol ether-di(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 0.1 parts by weight of hexamethylphosphoric triamine and 0.5 parts by weight of GPE10, continue stirring, and then sonicate to disperse evenly to obtain the desired spinning solution. (2) Using the above spinning solution, prepare fiber spinning membrane using an electrospinning device, place the spinning membrane in an oven at 55°C to evaporate the solvent, and obtain the desired sample; (3) Prepare a 2.2 mol / L lithium tetrafluoroborate solution, immerse the prepared spinning membrane in the lithium tetrafluoroborate solution, and then place the immersed membrane in an oven to evaporate the solvent to obtain an electrolyte membrane.

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