Search

CN-116931330-B - High-performance solid electrochromic polymer film and preparation method thereof

CN116931330BCN 116931330 BCN116931330 BCN 116931330BCN-116931330-B

Abstract

The invention belongs to the technical field of electrochromic polymer composite materials, and particularly relates to a high-performance solid electrochromic polymer film prepared by an electrostatic spinning method and a preparation method thereof. Electrochromic glass can be widely applied to various fields such as buildings, office meeting rooms, automobiles, aviation and the like. How to prepare a safety laminated glass with impact resistance and electrochromic is one of the key technologies in the field. In the invention, the solid electrochromic polymer film is prepared by an electrostatic spinning technology, and the material has excellent mechanical property and higher ionic conductivity. More importantly, the solid electrochromic polymer film has extremely small liquid content, greatly reduces the packaging difficulty, avoids the problems of environmental pollution caused by liquid electrolyte leakage and difficult packaging, and can be applied to the actual production of electrochromic glass in a large scale.

Inventors

  • WANG SHIWEI
  • WU YINGLI
  • WANG WEI
  • Yu Longjiao

Assignees

  • 长春工业大学

Dates

Publication Date
20260505
Application Date
20230705

Claims (11)

  1. 1. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 1 part by weight of chloroform, 50 parts by weight of DMF,10 parts by weight of polypyrrole and 8 parts by weight of polymethyl methacrylate into a reaction vessel, heating and stirring until the mixture is fully dissolved, adding 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, continuously stirring, and then carrying out ultrasonic dispersion to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a sodium chloride solution with the concentration of 3mol/L, soaking the spinning membrane prepared in the sodium chloride solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  2. 2. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 30 parts by weight of ethyl acetate, 1 part by weight of DMF (dimethyl formamide), 10 parts by weight of polyvinyl butyral into a reaction vessel, heating, stirring and fully dissolving, then adding 0.5 part by weight of methyl ethyl carbonate, 1 part by weight of triethylene glycol ether-bis (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate, 0.05 part by weight of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 0.5 part by weight of trioctyl phosphate and 0.5 part by weight of superfine silica, continuously stirring, and then dispersing uniformly by ultrasound to obtain a required spinning solution: (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a lithium phosphate solution with the concentration of 0.1mol/L, soaking the spinning membrane prepared in the lithium phosphate solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  3. 3. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 8 parts by weight of absolute ethyl alcohol, 30 parts by weight of DMF,10 parts by weight of ethylene oxide and 2 parts by weight of polyvinylidene fluoride into a reaction vessel, heating, stirring and fully dissolving, then adding 2 parts by weight of triethylene glycol diisooctyl ester, 0.05 part by weight of pentaerythritol tetrakis [ - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], 0.6 part by weight of ethylene glycol monostearate and 0.5 part by weight of DA-60, continuously stirring, and then carrying out ultrasonic dispersion to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a 1mol/L lithium perchlorate solution, soaking the spinning membrane prepared in the above in the lithium perchlorate solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain an electrolyte membrane.
  4. 4. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 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, heating and stirring until the mixture is fully dissolved, adding 0.08 part by weight of 1, 2-bis [ - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, 0.08 part by weight of 2-hydroxy-4-n-octoxybenzophenone and 0.8 part by weight of ethylene glycol monostearate, continuously stirring, and then carrying out ultrasonic dispersion until the mixture is uniformly dispersed to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a 2.5mol/L lithium hexafluorophosphate solution, soaking the spinning membrane prepared in the solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  5. 5. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 8 parts by weight of tetrahydrofuran, 30 parts by weight of thionyl chloride, 10 parts by weight of polyurethane and 2 parts by weight of polytetrafluoroethylene into a reaction vessel, heating and stirring to fully dissolve, then adding 2 parts by weight of diisooctyl adipate, 0.05 part by weight of triethylene glycol ether-bis (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid and 0.5 part by weight of 2- (5-chloro-2H-benzotriazole-2-yl) -4, 6-bis (1, 1-dimethylethyl) phenol, continuing stirring, and then carrying out ultrasonic dispersion to uniformly obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a lithium chloride solution with the concentration of 1.5mol/L, soaking the spinning membrane prepared in the lithium chloride solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  6. 6. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 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 into a reaction vessel, heating and stirring until the materials are fully dissolved, adding 3.5 parts by weight of diisononyl phthalate, 0.5 part by weight of tris (2, 4-di-tert-butylphenyl) phosphite, 0.05 part by weight of 2-hydroxy-4-1 octoxybenzophenone, 1.5 parts by weight of conductive graphite and 1.5 parts by weight of titanium dioxide, continuously stirring, and then carrying out ultrasonic dispersion until the materials are uniformly dispersed to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a 0.5mol/L lithium borate solution, soaking the spinning membrane prepared in the above in the lithium borate solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  7. 7. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 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 into a reaction vessel, heating and stirring until the mixture is fully dissolved, adding 3 parts by weight of triethylene glycol diisooctyl ester, 0.45 part by weight of 4,4' -thiobis (6-tertiary butyl-3-methylphenol, 0.35 part by weight of 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 0.5 part by weight of chloroprene rubber and 0.5 part by weight of tributyl phosphate, continuously stirring, and then uniformly dispersing the mixture by ultrasonic waves to prepare a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing 1.5mol/L lithium perchlorate solution, soaking the spinning film prepared in the above in the lithium perchlorate solution And (3) placing the soaked membrane in an oven to volatilize the solvent for 12 hours, so as to obtain the electrolyte membrane.
  8. 8. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 12 parts by weight of absolute ethyl alcohol, 28 parts by weight of DMF,10 parts by weight of polypyrrole and 5 parts by weight of polyvinylidene fluoride into a reaction vessel, heating and stirring until the materials are fully dissolved, adding 2.8 parts by weight of ethyl acetate, 0.35 part by weight of triethylene glycol ether-bis (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate, 0.05 part by weight of 2- (5-chloro-2H-benzotriazole-2-yl) -4, 6-bis (1, 1-dimethylethyl) phenol and 1 part by weight of ethylene glycol monostearate, continuously stirring, and then uniformly dispersing the materials by ultrasound to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a lithium phosphate solution with the concentration of 0.8mol/L, soaking the spinning membrane prepared in the lithium phosphate solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  9. 9. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 18 parts by weight of thionyl chloride, 22 parts by weight of DMF,10 parts by weight of poly (3, 4-ethylenedioxythiophene) and 4 parts by weight of ethylene oxide into a reaction vessel, heating and stirring until the materials are fully dissolved, adding 3 parts by weight of dioctyl phthalate, 0.25 part by weight of E-stearyl-propionate B- (3, 5-di-tert-butyl-4-hydroxyphenyl), 0.25 part by weight of hexamethylphosphoric triamide, 0.4 part by weight of ethylene glycol monostearate, 0.5 part by weight of dibasic lead phosphite and 0.3 part by weight of carbon black, continuously stirring, and then carrying out ultrasonic dispersion to obtain a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing a 2mol/L lithium hexafluorophosphate solution, soaking the spinning membrane prepared in the solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  10. 10. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) Adding 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 into a reaction vessel, heating and stirring until the components are fully dissolved, adding 2.8 parts by weight of diisooctyl adipate, 0.5 part by weight of 4,4' -thiobis (6-tert-butyl-3-methylphenol), 0.3 part by weight of 2- (5-chloro-2H-benzotriazole-2-yl) -4, 6-bis (1, 1-dimethylethyl) phenol and 1 part by weight of GPE10, continuously stirring, and then uniformly dispersing by ultrasound to prepare a required spinning solution; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing 1.8mol/L lithium hexafluoroarsenate solution, soaking the spinning membrane prepared in the solution of lithium hexafluoroarsenate, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.
  11. 11. A method for preparing a high performance solid state electrochromic polymer film, the method comprising the steps of: (1) 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 are added into a reaction vessel, heated and stirred until the components are fully dissolved, 3 parts by weight of dibutyl sebacate, 0.1 part by weight of triethylene glycol ether-bis (3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate, 0.1 part by weight of hexamethylphosphoric triamide and 0.5 part by weight of GPE10 are added, stirring is continued, and then ultrasonic treatment is carried out to uniformly disperse the components, so that the required spinning solution is prepared; (2) Preparing a fiber spinning film by using the spinning solution and adopting an electrostatic spinning device, and volatilizing the solvent of the spinning film in a 55 ℃ oven to obtain a required sample; (3) Preparing 2.2mol/L lithium tetrafluoroborate solution, soaking the spinning membrane prepared in the solution, and then placing the soaked membrane in an oven to volatilize the solvent to obtain the electrolyte membrane.

Description

High-performance solid electrochromic polymer film and preparation method thereof Technical Field The invention relates to the field of electrochromic materials, in particular to a high-performance solid electrochromic polymer film and a preparation method thereof. Background Electrochromic materials have reversible optical property changes under the drive of external voltage, and based on the optical characteristics, electrochromic materials and devices are widely applied to the fields of intelligent windows, goggles, antiglare rearview mirrors and the like. Along with the development of the age and the progress of technology, the functionality of electrochromic technology is continuously enhanced, a series of novel electrochromic materials and devices such as flexibility, dual-band, mid-far infrared and the like emerge, and the application of the electrochromic materials in the fields of intelligent clothing, aerospace, multicolor display and the like is expanded. However, most of the prior researches use liquid or gel electrolyte to assemble electrochromic devices, so that the problems of narrow electrochemical window, easy decomposition of high voltage, difficult packaging, inflammability, easy leakage and the like of the devices are caused. In comparison, the all-solid-state polymer electrolyte does not contain any organic solvent, has good mechanical property, high electrochemistry and thermal stability, and simple preparation process, and has great development potential, but the low ionic conductivity of the all-solid-state electrolyte limits the rapid development of the all-solid-state electrolyte. Therefore, developing an all-solid-state electrolyte that combines high permeability, flexibility, and ionic conductivity and that is applicable to electrochromic devices is a currently urgent problem to be solved. In practical applications, how to prepare electrochromic safety glass with impact resistance is one of the key technologies of the core. The preparation of glass with good impact resistance, light transmittance and rapid response speed is of great importance for further applications. The PVB porous electrolyte film is prepared by an electrostatic spinning method in the patent CN 107422564A, and is soaked in a lithium perchlorate propylene carbonate solution so as to improve the ionic conductivity and mechanical property, and the ionic conductivity of an electrolyte membrane is improved by modifying PMMA with propylene carbonate in the patent CN 111474792A. The electrolyte membrane prepared by the above technology has electrochromic characteristics, but laminated glass made from them cannot resist external strong impact and does not have safety characteristics. How to improve the impact resistance of electrochromic polymer films and endow better safety is a technical problem which needs to be solved in industry. Disclosure of Invention Aiming at the technical problems, the invention provides a solid electrochromic polymer film which not only has higher ionic conductivity, but also has excellent mechanical property and impact resistance, and the invention also aims to provide a method for producing the solid electrochromic polymer film, which has the advantages of simple process, easily controlled conditions and low production cost. In order to achieve the above purpose, the technical scheme of the invention is as follows: The invention provides a preparation method of a solid electrochromic polymer film, which comprises the steps of respectively preparing spinning solution, spinning film and electrolyte solution, soaking the spinning film into the electrolyte solution, and drying to obtain the solid electrochromic polymer film. Preferably, the solid electrochromic polymer film spinning process is as follows: the flow rate is 0.3-3 ml/h; the voltage is 3-50 kv; spinning time is 0.5-24 hours; The distance between the needle head and the receiver is 3-50 cm; the spinning environment temperature is-10-85 ℃; The ambient humidity is 2-90%. The invention also provides a preparation method of the solid electrochromic polymer film, which comprises the following steps: (1) Adding a certain amount of a solvent A and a certain amount of a solvent B into a container, then adding a polymer A and a polymer B, heating and stirring for 9-24 hours at a temperature above 60 ℃ to fully dissolve, adding a certain amount of a plasticizer, an antioxidant and an ultraviolet light absorber, continuously stirring for 3-6 hours at a temperature above 60 ℃, and then carrying out ultrasonic treatment for 10-30 minutes to uniformly disperse the mixture to obtain a required spinning solution, wherein the spinning solution comprises the following components of 100 parts (by weight) of the polymer A, 0-80 parts (by weight) of the polymer B, 10-300 parts (by weight) of the solvent A, 10-500 parts (by weight) of the solvent B, 5-50 parts (by weight) of the plasticizer, 0-10 parts (by weight) of the antioxidant, 0-10 parts (by wei