A hybrid ionic electronic conductive polymer material and a preparation method and application thereof

Abstract

The application belongs to the field of conductive functional polymer materials, and particularly relates to a mixed ionic and electronic conductive polymer material and a preparation method and application thereof. In view of the problems of slow charge transmission, response lag, low efficiency and short cycle life caused by the mismatch between ion and electron transmission in existing solid-state devices, the mixed ionic and electronic conductive polymer with intrinsic ion-electron dual-channel characteristics is prepared through a rigid-flexible structure design and a conjugate structure breaking synthesis strategy, and a universal and controllable preparation approach for customized development of high-performance electrochromic polymers is provided. The mixed ionic and electronic conductive polymer provided by the application can be simultaneously applied in an electrochromic visual energy storage window to realize high integration of light regulation and electrical energy storage, and in an electrochromic visual organic electrochemical transistor to realize integration and cooperation of light modulation function and signal amplification function, and exhibits wide application potential as a core functional material.

Description

Technical Field

[0001] This belongs to the field of conductive functional polymer materials, specifically involving a mixed ionic and electronic conductive polymer material, its preparation method, and its application. Background Technology

[0002] Electrochromic polymer materials have attracted widespread attention from industry and academia due to their unique electrochemically driven color-switching characteristics and tunable photophysical properties. With the increasing demands for functional integration in modern devices, electrochromic technology is undergoing significant evolution. This comprehensive integration strategy is driving the development of a new generation of high-performance quasi-solid-state electrochromic devices, with enhanced device integration potential and environmental friendliness / safety being key driving factors. However, solid-state electrochromic devices still face the significant challenge of slow electron and ion transport at the interface between the electrochromic layer and the solid electrolyte, as well as within the electrochromic layer itself.

[0003] In recent years, researchers have effectively improved the ionic conductivity of materials by introducing polar segments into the polymer backbone or incorporating inorganic nanoparticles into the electrolyte system, thereby accelerating ion migration and significantly optimizing the response characteristics and cycling stability of quasi-solid-state electrochromic devices. Furthermore, using metal-organic frameworks as structure-directed dopants or precisely selecting anions with strong delocalization capabilities to modify conjugated polymers at the molecular level can significantly optimize their electronic structure, thereby improving response speed and optical contrast. However, in all quasi-solid-state electrochromic devices, the electrode / electrolyte interface lacks liquid-mediated wetting, resulting in a complex solid-solid contact interface that forces electrons / ions to transport along tortuous paths. Simultaneously, optimization strategies that solely improve electronic or ionic conductivity may lead to interfacial charge accumulation due to electron-ion transport rate mismatch, ultimately resulting in synergistic failure mechanisms such as electrochemical polarization and cycling decay. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of slow charge transport, mismatch between ion and electron transport leading to sluggish response, low efficiency and short cycle life in existing solid-state devices. It provides a hybrid ion-electron conductive polymer material with a "rigid-flexible" molecular structure, its preparation method and its application in visual electrochromic energy storage windows and visual electrochromic organic electrochemical transistors.

[0005] The technical solution of this invention is as follows:

[0006] A first aspect of the present invention provides a hybrid ion- and electron-conductive polymer material, the main chain of which is both an electronic conductor and an ion conductor, the polymer having repeating units with the structure shown in formula (I):

[0007]

[0008] Equation (I)

[0009] Where n is a positive integer, representing the degree of aggregation.

[0010] A second aspect of the present invention provides a method for preparing a mixed ion-electron conductive polymer material, comprising the following steps:

[0011] Step A: Monomer synthesis:

[0012] A1: Under a nitrogen atmosphere, add 4-hydroxydiphenylamine and sodium hydroxide to a three-necked round-bottom flask containing DMF solvent, and stir mechanically for 1 hour;

[0013] A2: Add solid potassium iodide to the solution in step A1 above and stir mechanically for 15 minutes;

[0014] A3: Add diethylene glycol dichloroethyl ester to the solution in step A2 above, and heat and stir for 12 hours;

[0015] A4: Transfer the mixed solution after the reaction in step A3 to a separatory funnel, and extract the organic layer six times with saturated sodium chloride solution and dichloromethane solution to obtain the organic phase;

[0016] A5: The organic phase obtained in step A4 is concentrated under reduced pressure and then dried in a vacuum dryer at 60°C to obtain a brown solid.

[0017] Step B: Synthesis of mixed ionic and electronically conductive polymers:

[0018] B1: Add the monomer synthesized in step A and p-phenylenediamine to a round-bottom flask containing DMF solvent in sequence, and stir mechanically for 10 minutes.

[0019] B2: Add 3 mol / L hydrochloric acid solution dropwise to the solution obtained in step B1 under stirring conditions, and stir mechanically until a uniform dispersion is formed;

[0020] B3: Add solid ammonium persulfate to a 3 mol / L hydrochloric acid solution, and then add the hydrochloric acid solution containing ammonium persulfate dropwise to the dispersion obtained in step B2 under stirring. React at room temperature for 24 hours.

[0021] B4: After the reaction in step B3 is completed, the mixed solution is transferred to ice water to precipitate, then filtered. The precipitate is then washed successively with distilled water, ethanol and dichloromethane until it is colorless, to obtain the oxidized mixed ionic electronic conductive polymer.

[0022] B5: Disperse the oxidized mixed ionic conductive polymer obtained in step B4 in an ammonia solution, add hydrazine hydrate for reduction, and then transfer it to a vacuum oven at 45°C to dry for 24 hours to obtain a dark blue solid.

[0023] Further, in step A1, the molar ratio of 4-hydroxydiphenylamine to diethylene glycol dichloroethyl ester in step A3 is 2.5:1; in step B1, the molar ratio of monomer to p-phenylenediamine is 1:1; and in step B5, the molar ratio of the oxidized mixed ionic conductive polymer to hydrazine hydrate is 1:6.

[0024] A third aspect of the present invention provides an application of a hybrid ion-electron conductive polymer material in an electrochromic visualization energy storage window, comprising the following steps:

[0025] Step 1: Prepare the mixed ion-electro-conducting polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte;

[0026] Step 2: Assemble the mixed ion-electron conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode and gel electrolyte obtained in Step 1 into a sandwich structure and bond them together with photocurable adhesive.

[0027] Step 3: Attach the copper strip to the positive and negative poles of the sandwich structure described in Step 2 to obtain the electrochromic visualization energy storage window.

[0028] Furthermore, the preparation method of the mixed ion-electro-conducting polymer / ITO working electrode described in step one includes the following steps:

[0029] Step 1: Dissolve the mixed ionic and electronically conductive polymer in DMF solvent to prepare a homogeneous solution;

[0030] Step 2: Spray the solution obtained in Step 1 onto an ITO glass substrate at 200℃ to obtain a mixed ion-electron conductive polymer / ITO working electrode.

[0031] Furthermore, the method for preparing the vanadium pentoxide / ITO counter electrode described in step one includes the following steps:

[0032] Step 1: Dissolve vanadium pentoxide and sodium chloride in deionized water at 60℃, and heat and stir until the color changes from yellow to brown;

[0033] Step 2: Centrifuge the mixture obtained in Step 1 three times at 6000 r / min, wash with deionized water and ethanol until colorless, and collect the precipitate;

[0034] Step 3: Transfer the precipitate obtained in Step 2 to a vacuum oven at 45°C and dry for 24 hours to obtain V2O5 nanowires;

[0035] Step 4: Disperse the V2O5 nanowires described in Step 3 uniformly in deionized water, and then spin-coat the solution onto an ITO glass substrate at a speed of 2000 r / min for 30 seconds to form a uniform thin film.

[0036] Step 5: Anneal at 60℃ for 1 hour to obtain vanadium pentoxide / ITO counter electrode.

[0037] A fourth aspect of the present invention provides the application of a hybrid ion- and electron-conductive polymer material in an electrochromic visualization organic electrochemical transistor, comprising the following steps:

[0038] Step 1: Dissolve the mixed ionic and electronically conductive polymer in DMF solvent to prepare a homogeneous solution;

[0039] Step 2: Spray the solution obtained in Step 1 onto the interdigitated gold electrode at 200℃;

[0040] Step 3: Spin-coat the gel electrolyte onto the interdigitated gold electrode prepared in step 2 to form a uniform thin film. The intersection region of the interdigitated electrode constitutes the source and drain of the transistor.

[0041] Furthermore, the application of the above-mentioned mixed ion-electron conductive polymer material in electrochromic visualization energy storage windows and electrochromic visualization organic electrochemical transistors, wherein the preparation of the gel electrolyte includes the following steps:

[0042] Step 1: Dissolve polyethylene oxide in acetonitrile to prepare a homogeneous solution;

[0043] Step 2: Add anhydrous propylene carbonate and lithium perchlorate to the solution from Step 1, and stir for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

[0044] The beneficial effects of this invention are:

[0045] 1. This invention prepares a mixed ion-electron conductive polymer with intrinsic ion-electron dual-channel characteristics through a "rigid-flexible" structural design and a "conjugate structure breaking method" synthesis strategy. Furthermore, the material properties can be adjusted through modular design, providing a universal and controllable preparation route for the customized development of high-performance electrochromic polymers.

[0046] 2. The hybrid ion-electron conductive polymer provided by this invention solves the core bottleneck of ion-electron transport mismatch in solid-state devices and has been successfully applied to the field of electrochromic visualization energy storage windows. It achieves a high degree of integration of light regulation and energy storage, which can not only intelligently regulate indoor light and temperature and greatly improve building energy efficiency, but also recycle and utilize the stored solar energy, providing key technical support for realizing the integrated system of "intelligent building-energy management".

[0047] 3. The hybrid ionic electronic conductive polymer provided by this invention has been successfully applied in electrochromic visualization organic electrochemical transistors, realizing the integrated synergy of optical modulation function and signal amplification function. The fabricated device can intuitively quantify the signal gain intensity through color gradient changes, and establishes a real-time mapping relationship between optical response and electrical amplification, providing an innovative technical path for the development of intelligent sensing and display integrated systems. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely embodiments of the present invention, and those skilled in the art can obtain other drawings based on the provided drawings without creative effort.

[0049] Figure 1 The mixed ionic electron monomer prepared in Example 1 of this invention 1 H NMR spectrum;

[0050] Figure 2 The image shows the FTIR spectrum of the mixed ionic electron monomer prepared in Example 1 of this invention.

[0051] Figure 3 The mixed ionic and electronically conductive polymer prepared in Example 1 of this invention 1 H NMR spectrum;

[0052] Figure 4 The FTIR spectrum of the mixed ionic-electron conductive polymer prepared in Example 1 of this invention;

[0053] Figure 5 The non-mixed ionic electronic monomer prepared in Comparative Example 1 of this invention 1 H NMR spectrum;

[0054] Figure 6 The non-mixed ionic electronically conductive polymer prepared in Comparative Example 1 of this invention 1 H NMR spectrum;

[0055] Figure 7 The TGA curve of the mixed ionic and electronically conductive polymer prepared in Example 1 of this invention;

[0056] Figure 8 The conductivity diagrams are for the mixed ionic and electronically conductive polymers and the non-mixed ionic and electronically conductive polymers prepared in Example 1 and Comparative Example 1 of this invention.

[0057] Figure 9This is a CV curve of the mixed ion-electro-conducting polymer / ITO working electrode prepared in Example 1 of the present invention at different scan rates in a three-electrode system;

[0058] Figure 10 The graph shows the transmittance variation of the mixed ion-electron conductive polymer / ITO working electrode prepared in Example 1 of this invention at voltages of -0.5 to 0.9 V.

[0059] Figure 11 The graph shows the transmittance variation of the non-mixed ionic conductive polymer / ITO working electrode prepared in Comparative Example 1 of this invention at voltages of -0.5 to 0.9 V.

[0060] Figure 12 The image shows the CV curves of the electrochromic visualization energy storage window prepared in Example 2 of this invention at different scan rates.

[0061] Figure 13 The transmittance variation curve of the electrochromic visualization energy storage window prepared in Example 2 of the present invention under voltages of 0V to 1.8V;

[0062] Figure 14 The image shows the transmittance variation curve of the electrochromic visualization energy storage window prepared in Comparative Example 2 of this invention under voltages of 0V to 1.8V.

[0063] Figure 15 The image shows the transmittance change of the electrochromic visualization energy storage window prepared in Example 2 of this invention during the application of a 15000th power square wave voltage.

[0064] Figure 16 This is a constant current charge-discharge curve of the electrochromic visualization energy storage window prepared in Example 2 of the present invention;

[0065] Figure 17 The constant current charge-discharge curve of the electrochromic visualization energy storage window prepared in Comparative Example 2 of this invention is shown.

[0066] Figure 18 The transmittance-energy storage performance diagram of the electrochromic visualization energy storage window prepared in Example 2 of the present invention;

[0067] Figure 19 The output characteristic curve of the electrochromic visual organic electrochemical transistor prepared in Example 3 of the present invention is shown.

[0068] Figure 20 The output characteristic curve of the electrochromic organic electrochemical transistor prepared in Comparative Example 3 of this invention is shown.

[0069] Figure 21 Electrochromic image of the electrochromic visualization organic electrochemical transistor prepared in Example 3 of this invention;

[0070] Figure 22 This is a relaxation time distribution diagram of the electrochromic visualization energy storage window prepared in Example 2 of the present invention during the charging and discharging process;

[0071] Figure 23 This is a relaxation time distribution diagram of the electrochromic visualization energy storage window prepared in Comparative Example 4 of the present invention during the charging and discharging process. Detailed Implementation

[0072] To make the objectives, technical effects, and technical solutions of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention. Based on the embodiments disclosed in the present invention, other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0073] Example 1

[0074] This invention provides a method for preparing a mixed ionic-electron conductive polymer material, comprising the following steps:

[0075] Step A: Monomer synthesis:

[0076] A1: Under a nitrogen atmosphere, add 4-hydroxydiphenylamine (1.85 g, 10 mmol) and sodium hydroxide (0.64 g, 16 mmol) to a three-necked round-bottom flask containing 30 mL of DMF, and stir for 1 hour;

[0077] A2: Add potassium iodide solid (1.59 g, 9.6 mmol) to the solution in step A1 above and stir mechanically for 15 minutes;

[0078] A3: Add diethylene glycol dichloroethyl ester (0.9 g, 4 mmol) to the solution in step A2 above, and heat and stir for 12 hours;

[0079] A4: Transfer the mixed solution after the reaction in step A3 to a 500 mL separatory funnel, and extract the organic layer six times with 100 mL saturated sodium chloride solution and 100 mL dichloromethane solution to obtain the organic phase;

[0080] A5: The organic phase obtained in step A4 is concentrated under reduced pressure and then dried in a vacuum dryer at 60°C to obtain a brown solid.

[0081] Step B: Synthesis of mixed ionic and electronically conductive polymers:

[0082] B1: Add the monomer (1.05 g, 2 mmol) and p-phenylenediamine (0.22 g, 2 mmol) synthesized in step A to a round-bottom flask containing 40 mL of DMF solvent, and stir mechanically for 10 minutes.

[0083] B2: Add 15 mL of 3 mol / L hydrochloric acid solution dropwise to the solution obtained in step B1 under stirring conditions, and stir mechanically until a uniform dispersion is formed;

[0084] B3: Add 0.40 g (1.74 mmol) of ammonium persulfate solid to 10 mL of 3 mol / L hydrochloric acid solution, and then add the hydrochloric acid solution containing ammonium persulfate dropwise to the dispersion obtained in step B2 under stirring. React at room temperature for 24 hours.

[0085] B4: After the reaction in step B3 is completed, transfer the mixed solution to 300 mL of ice water to precipitate, then filter it. After obtaining the precipitate, wash it successively with distilled water, ethanol and dichloromethane until it is colorless, and obtain the oxidized mixed ionic electronic conductive polymer.

[0086] B5: The oxidized mixed ionic conductive polymer obtained in step B4 was dispersed in a 2.5 mol / L ammonia solution, hydrazine hydrate was added for reduction, and then the mixture was transferred to a vacuum oven at 45°C and dried for 24 hours to obtain a dark blue solid.

[0087] The structural formula and preparation reaction formula of the above-mentioned mixed ionic and electronically conductive polymer material are as follows:

[0088]

[0089] Example 2

[0090] This embodiment provides a method for fabricating an electrochromic visualization energy storage window device based on a hybrid ion-electron conductive polymer, comprising the following steps:

[0091] Step 1: Prepare the mixed ion-electro-conducting polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte;

[0092] Step 2: Assemble the mixed ion-electron conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode and gel electrolyte obtained in Step 1 into a sandwich structure and bond them together with photocurable adhesive.

[0093] Step 3: Attach the copper strip to the positive and negative poles of the sandwich structure described in Step 2 to obtain the electrochromic visualization energy storage window.

[0094] The preparation steps for the mixed ion-electron conductive polymer / ITO working electrode in step one are as follows:

[0095] 10 mg of the mixed ion-electron conductive polymer was dissolved in 1 mL of DMF to prepare a homogeneous solution; then the solution was sprayed onto an ITO glass substrate at 200 °C to obtain the mixed ion-electron conductive polymer / ITO working electrode.

[0096] The steps for preparing the vanadium pentoxide / ITO counter electrode in step one are as follows:

[0097] At 60℃, 1.0 g of vanadium pentoxide and 1.2 g of NaCl were dissolved in 100 mL of deionized water and stirred for 36 hours until the color changed from yellow to brown. The mixture was then centrifuged three times at 6000 r / min, washed with deionized water and ethanol until colorless, and the precipitate was collected. The precipitate was transferred to a vacuum oven at 45℃ and dried for 24 hours to obtain V2O5 nanowires. 2 mg of V2O5 nanowires were uniformly dispersed in 5 mL of deionized water, and the solution was then spin-coated onto an ITO glass substrate at 2000 r / min for 30 seconds to form a uniform thin film. Finally, the film was annealed at 60℃ for 1 hour to obtain a vanadium pentoxide / ITO counter electrode.

[0098] The preparation of the gel electrolyte in step one includes the following steps:

[0099] 2.4 g of polyethylene oxide was dissolved in 10 mL of acetonitrile to prepare a homogeneous solution; 2.7 mL of anhydrous propylene carbonate and 1.06 g of lithium perchlorate were added to the solution, and the mixture was stirred for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

[0100] Example 3

[0101] This embodiment provides a method for fabricating an electrochromic visualization organic electrochemical transistor based on a hybrid ionic-electron conductive polymer, comprising the following steps:

[0102] Step 1: Dissolve 10 mg of the mixed ionic and electronically conductive polymer in 1 mL of DMF to prepare a homogeneous solution;

[0103] Step 2: Spray the solution obtained in Step 1 onto the interdigitated gold electrode at 200℃;

[0104] Step 3: Spin-coat the gel electrolyte onto the interdigitated gold electrode prepared in step 2 to form a uniform thin film. The intersection region of the interdigitated electrode constitutes the source and drain of the transistor.

[0105] The preparation of the gel electrolyte in step three includes the following steps:

[0106] 2.4 g of polyethylene oxide was dissolved in 10 mL of acetonitrile to prepare a homogeneous solution; 2.7 mL of anhydrous propylene carbonate and 1.06 g of lithium perchlorate were added to the solution, and the mixture was stirred for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

[0107] Comparative Example 1

[0108] This comparative example provides the synthesis of a non-mixed ionic electronically conductive polymer, comprising the following steps:

[0109] Step A: Monomer synthesis:

[0110] A1: Under a nitrogen atmosphere, add 4-hydroxydiphenylamine (3.70 g, 20 mmol) and potassium carbonate (4.41 g, 32 mmol) to a three-necked round-bottom flask containing 30 mL of DMF, and stir at room temperature for 1 hour;

[0111] A2: Add potassium iodide (3.32 g, 20 mmol) and 1,11-dibromoundecane (2.51 g, 8 mmol) sequentially to the above solution.

[0112] A3: Heat the reaction system to 85°C and stir for 24 hours;

[0113] A4: Transfer the mixed solution after the reaction to a separatory funnel and extract it three times with 100 mL of saturated sodium chloride solution and 100 mL of dichloromethane solution;

[0114] A5: The obtained organic phase was concentrated under reduced pressure and then purified by column chromatography using dichloromethane / ethyl acetate (volume ratio 2:1) as eluent to obtain a white powdery solid with the following structural formula;

[0115]

[0116] Step B: Synthesis of non-mixed ionic electronically conductive polymers:

[0117] B1: Add the monomer (1.03 g, 2 mmol) synthesized in step A and p-phenylenediamine (0.22 g, 2 mmol) to a round-bottom flask containing 40 mL of DMF solvent, and stir mechanically for 10 minutes.

[0118] B2: During stirring, 15 mL of 3 mol / L hydrochloric acid solution is added dropwise to the above DMF solution to form a uniform dispersion;

[0119] B3: Add 0.40 g (1.74 mmol) of ammonium persulfate solid to 10 mL of 3 mol / L hydrochloric acid solution, and then add the hydrochloric acid solution containing ammonium persulfate dropwise to the dispersion obtained in step B2 under stirring. React at room temperature for 24 hours.

[0120] B4: After the reaction in step B3 is completed, transfer the mixed solution to 300 mL of ice water to precipitate, then filter it. Wash the precipitate with distilled water, ethanol and dichloromethane in sequence until it is colorless.

[0121] B5: The precipitate obtained in step B4 was dispersed in a 2.5 mol / L ammonia solution, hydrazine hydrate was added for reduction, and then the precipitate was transferred to a vacuum oven at 45°C and dried for 24 hours to obtain a dark blue solid with the following structural formula.

[0122]

[0123] Comparative Example 2

[0124] This embodiment provides a method for fabricating an electrochromic visualization energy storage window device based on a non-mixed ionic-electron conductive polymer, comprising the following steps:

[0125] Step 1: Prepare the non-mixed ionic electronically conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte;

[0126] Step 2: Assemble the non-mixed ionic conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte obtained in Step 1 into a sandwich structure and bond them together with photocurable adhesive.

[0127] Step 3: Attach the copper strip to the positive and negative poles of the sandwich structure described in Step 2 to obtain the electrochromic visualization energy storage window.

[0128] The preparation steps for the non-mixed ionic electronic conductive polymer / ITO working electrode in step one are as follows:

[0129] 10 mg of the non-mixed ionic conductive polymer was dissolved in 1 mL of DMF to prepare a homogeneous solution; then the solution was sprayed onto an ITO glass substrate at 200 °C to obtain the non-mixed ionic conductive polymer / ITO working electrode.

[0130] The steps for preparing the vanadium pentoxide / ITO counter electrode in step one are as follows:

[0131] At 60℃, 1.0 g of vanadium pentoxide and 1.2 g of NaCl were dissolved in 100 mL of deionized water and stirred for 36 hours until the color changed from yellow to brown. The mixture was then centrifuged three times at 6000 r / min, washed with deionized water and ethanol until colorless, and the precipitate was collected. The precipitate was transferred to a vacuum oven at 45℃ and dried for 24 hours to obtain V2O5 nanowires. 2 mg of V2O5 nanowires were uniformly dispersed in 5 mL of deionized water, and the solution was then spin-coated onto an ITO glass substrate at 2000 r / min for 30 seconds to form a uniform thin film. Finally, the film was annealed at 60℃ for 1 hour to obtain a vanadium pentoxide / ITO counter electrode.

[0132] Comparative Example 3

[0133] This embodiment provides a method for fabricating an electrochromic visualization organic electrochemical transistor based on a non-mixed ionic electronically conductive polymer, comprising the following steps:

[0134] Step 1: Dissolve 10 mg of the non-mixed ionic conductive polymer in 1 mL of DMF to prepare a homogeneous solution;

[0135] Step 2: Spray the solution obtained in Step 1 onto the interdigitated gold electrode at 200℃;

[0136] Step 3: Spin-coat the gel electrolyte onto the interdigitated gold electrode prepared in step 2 to form a uniform thin film. The intersection region of the interdigitated electrode constitutes the source and drain of the transistor.

[0137] The preparation of the gel electrolyte in step three includes the following steps:

[0138] 2.4 g of polyethylene oxide was dissolved in 10 mL of acetonitrile to prepare a homogeneous solution; 2.7 mL of anhydrous propylene carbonate and 1.06 g of lithium perchlorate were added to the solution, and the mixture was stirred for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

[0139] Comparative Example 4

[0140] This embodiment provides a method for fabricating an electrochromic visualization energy storage window device based on a hybrid ion-electron conductive polymer, comprising the following steps:

[0141] Step 1: Prepare the mixed ion-electro-conducting polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte;

[0142] Step 2: Assemble the mixed ion-electron conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode and gel electrolyte obtained in Step 1 into a sandwich structure and bond them together with photocurable adhesive.

[0143] Step 3: Attach the copper strip to the positive and negative poles of the sandwich structure described in Step 2 to obtain the electrochromic visualization energy storage window.

[0144] The preparation steps for the mixed ion-electron conductive polymer / ITO working electrode in step one are as follows:

[0145] 10 mg of the mixed ion-electron conductive polymer was dissolved in 1 mL of DMF to prepare a homogeneous solution; then the solution was sprayed onto an ITO glass substrate at 200 °C to obtain the mixed ion-electron conductive polymer / ITO working electrode.

[0146] The steps for preparing the vanadium pentoxide / ITO counter electrode in step one are as follows:

[0147] At 60℃, 1.0 g of vanadium pentoxide and 1.2 g of NaCl were dissolved in 100 mL of deionized water and stirred for 36 hours until the color changed from yellow to brown. The mixture was then centrifuged three times at 6000 r / min, washed with deionized water and ethanol until colorless, and the precipitate was collected. The precipitate was transferred to a vacuum oven at 45℃ and dried for 24 hours to obtain V2O5 nanowires. 2 mg of V2O5 nanowires were uniformly dispersed in 5 mL of deionized water, and the solution was then spin-coated onto an ITO glass substrate at 2000 r / min for 30 seconds to form a uniform thin film. Finally, the film was annealed at 60℃ for 1 hour to obtain a vanadium pentoxide / ITO counter electrode.

[0148] Unlike Example 2, the preparation of the gel electrolyte in step one includes the following steps:

[0149] 2.4 g of polymethyl methacrylate was dissolved in 10 mL of acetonitrile to prepare a homogeneous solution; 2.7 mL of anhydrous propylene carbonate and 1.06 g of lithium perchlorate were added to the solution, and the mixture was stirred for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

[0150] Figure 1 The mixed ionic-electron polymer monomer prepared in Example 1 of this invention 1 The 1H NMR spectrum shows that the characteristic signal of -NH is around 7.86 ppm, aromatic hydrogens are between 6 ppm and 8 ppm, and hydrogens on common alkyl chains are between 3 ppm and 4 ppm.

[0151] Figure 2 This is the FTIR spectrum of the mixed ionic-electron polymer monomer prepared in Example 1 of this invention. The stretching vibration peak of the amide appears at 3386 cm⁻¹. -1 The absorption peak of the CH stretching vibration of the benzene ring appears at 2957 cm⁻¹. -1 The C=C tensile vibration peak on the benzene ring appears at 1508-1598 cm⁻¹. -1Within the range, the tensile vibration peaks of CN and COC appeared at 1241 cm⁻¹. -1 and 1103cm -1 Place.

[0152] Figure 3 The mixed ionic and electronically conductive polymer prepared in Example 1 of this invention 1 The 1H NMR spectrum shows the characteristic signal of -NH around 7.84 ppm, aromatic hydrogens between 6 and 8 ppm, and hydrogens on common alkyl chains between 3 and 4 ppm. Compared to the monomer, the polymer exhibits less pronounced aromatic hydrogen peak splitting, confirming the successful preparation of the mixed ionic-electron polymer.

[0153] Figure 4 The image shows the FTIR spectrum of the mixed ionic-electron conductive polymer prepared in Example 1 of this invention. The stretching vibration peak of the amide appears at 3386 cm⁻¹. -1 The absorption peak of the CH stretching vibration of the benzene ring appears at 2957 cm⁻¹. -1 The C=C tensile vibration peak on the benzene ring appears at 1508-1598 cm⁻¹. -1 Within the range, the tensile vibration peaks of CN and COC appeared at 1241 cm⁻¹. -1 and 1103cm -1 Place.

[0154] Figure 5 The non-mixed ionic electron polymer monomer prepared in Comparative Example 1 of this invention 1 The 1H NMR spectrum shows the characteristic signal of -NH around 7.86 ppm, aromatic hydrogens between 6 and 8 ppm, and hydrogens on common alkyl chains around 3.89 and 1.81 ppm. The non-mixed ionic monomers exhibit a peak at 1.81 ppm compared to the mixed ionic monomers.

[0155] Figure 6 The non-mixed ionic electronically conductive polymer prepared in Comparative Example 1 of this invention 1 The 1H NMR spectrum shows the characteristic signal of -NH around 7.86 ppm. Aromatic hydrogens are located between 6 ppm and 8 ppm. Hydrogens on common alkyl chains are located around 3.89 ppm and 1.81 ppm. Compared with monomers without mixed ionic electrons, the polymer's aromatic hydrogen peaks show less splitting, demonstrating the successful preparation of polymers without mixed ionic electrons.

[0156] Figure 7The TGA curve of the mixed ionic and electronically conductive polymer prepared in Example 1 of this invention is shown. The thermal stability of the polymer was investigated using TGA under nitrogen atmosphere. The temperature at which the baseline intersects the tangent of the thermogravimetric curve at the point of maximum slope is defined as the initial decomposition temperature (T0). d The temperature at which the compound loses 5% of its mass is T. 5% 损失 The TGA curve shows the T0 of the mixed ionic electronically conductive polymer. d The temperature was 201.75℃, T 5% 损失 The temperature was 288.83℃, which indicates that the prepared polymer has relatively good thermodynamic stability, providing safety for its application in high-temperature environments.

[0157] Figure 8 The diagram shows the conductivity of the polymers prepared in Example 1 and Comparative Example 1 of this invention. The electronic conductivity of the mixed ionic-electron conductive polymer prepared in Example 1 ranges from 9.5 × 10⁻⁶. -3 Up to 7.5×10 -2 S cm -1 The ionic conductivity consistently exceeds 6.4 × 10⁻⁶. -4 S cm -1 In contrast, the electronic conductivity of the non-mixed ionic electronically conductive polymer is 1.7 × 10⁻⁶. -5 Up to 5.4×10 -3 S cm -1 And the ionic conductivity is less than 5.9 × 10⁻⁶. -6 S cm -1 This demonstrates that the ion-electron synergistic transport characteristics exhibited by the hybrid ion-electron conductive polymer highlight the significant ion-electrocoupling effect of this material in electrochemical processes, laying a crucial foundation for the high-performance optimization of electrochromic visualization energy storage windows and electrochromic visualization organic electrochemical transistors.

[0158] Figure 9 The mixed ion-electro-conducting polymer / ITO working electrode prepared in Example 1 of this invention is used in a three-electrode configuration (1M LiClO4 / acetonitrile as electrolyte, mixed ion-electro-conducting polymer / ITO as working electrode, Ag / Ag...). + CV curves (scan rate 10 mV / s) were tested in a system with the electrode as the reference electrode and the Pt wire as the counter electrode at different scan rates. -1 Up to 100mV s -1 (Voltage window: -0.5V to 0.9V). A pair of redox peaks are shown on the curve at 0.27V / -0.07V. Furthermore, the peak shape of the CV curve also indicates that the hybrid ion-electron conductive polymer / ITO working electrode has good energy storage performance.

[0159] Figure 10 The transmittance curves of the mixed ion-conducting polymer / ITO working electrode prepared in Example 1 of this invention are shown in the voltage range of -0.5 to 0.9 V. The mixed ion-conducting polymer / ITO working electrode exhibits high transmittance in both the visible and near-infrared regions. The maximum transmittance at 670 nm and 1300 nm are 76.98% and 70.23%, respectively. The transmittance of the mixed ion-conducting polymer / ITO working electrode changes significantly after applying different voltages, which should be attributed to the redox state transition of the aniline segment during the electrochemical process.

[0160] Figure 11 The transmittance curves of the non-mixed ionic conductive polymer / ITO working electrode prepared in Comparative Example 1 of this invention are obtained by coupling an electrochemical workstation with a UV-Vis-NIR spectrometer. The transmittance of the non-mixed ionic conductive polymer / ITO working electrode prepared in Comparative Example 2 is 49.82%, demonstrating the excellent electrochromic properties of the mixed ionic conductive polymer prepared in Example 1.

[0161] Figure 12 The image shows the CV curves of the electrochromic visualization energy storage window prepared in Example 2 of this invention at different scan rates. (At 10 mV / s) -1 Up to 100mV s -1 At the specified scan rate, the voltage window of the energy storage window can reach 1.8V, and the redox peak current of the electrochromic energy storage window gradually increases with the increase of the scan rate, revealing its excellent electrochemical kinetics. Similarly, the shape of the CV curve also shows that the energy storage window has excellent energy storage performance.

[0162] Figure 13 The image shows the transmittance variation curve of the electrochromic visualization energy storage window prepared in Example 2 of this invention under voltages ranging from 0V to 1.8V. The electrochromic capacitive window exhibits significant transmittance variations in both the visible and near-infrared regions, with peak transmittances of 68.9% and 71.5% at 680nm and 1230nm, respectively. This demonstrates that the electrochromic visualization energy storage window can achieve dual-band modulation of visible light and solar radiation during the transition between 0V and 1.8V.

[0163] Figure 14 For Comparative Example 2 of this invention, the transmittance variation curves of the electrochromic visualization energy storage window were prepared under voltages ranging from 0V to 1.8V. The highest transmittances at 700nm and 1215nm were 52.02% and 56.71%, respectively, indicating the excellent electrochromic energy storage window performance of the mixed ion-electron conductive polymer.

[0164] Figure 15 This image shows the transmittance change of the electrochromic visualization energy storage window prepared in Example 2 of this invention during the application of a 15,000-fold square wave voltage. Under alternating voltage conditions of 0V and 1.8V, its optical durability was studied using an electrochemical workstation paired with a UV-Vis-NIR spectrometer. After 15,000 cycles, the transmittance of the electrochromic visualization energy storage window only decreased to 86.7% of its initial value. This data strongly confirms the feasibility of this electrochromic capacitive window in long-term use scenarios.

[0165] Figure 16 This is a constant current charge-discharge curve of the electrochromic visualization energy storage window prepared in Example 2 of the present invention. At a current density of 0.1 mA cm⁻², the single charge-discharge cycle time is significantly extended to 5175 seconds. This demonstrates the outstanding energy storage performance of the electrochromic visualization energy storage bed prepared from the mixed ion-electron conductive polymer.

[0166] Figure 17 This is a constant current charge-discharge curve of the electrochromic visualization energy storage window prepared in Comparative Example 2 of this invention. At a current density of 0.1 mA cm⁻², the single charge-discharge cycle time is less than 2500 s, directly verifying the rationality of the hybrid ion-electron conductive polymer molecular structure design, confirming that it effectively improves ion / electron transport efficiency and promotes a more complete redox reaction.

[0167] Figure 18 This is a transmittance-energy storage performance diagram of the electrochromic visualization energy storage window prepared in Example 2 of this invention. The testing device cleverly integrates an electrochemical workstation and a UV-Vis-NIR spectrophotometer, enabling real-time monitoring of the evolution of optical transmittance during charging and discharging. The experimental results clearly reveal the strong correlation between charge accumulation and optical modulation. During the charging phase, as the charge inside the electrochromic visualization energy storage window continues to accumulate, its optical transmittance gradually decreases, reaching an absolute minimum under full charge. During the discharging phase, the opposite trend is observed, with transmittance gradually recovering as the charge dissipates, eventually returning to the initial high transmittance state. Throughout the entire charging and discharging cycle, the charge storage state and optical response behavior exhibit a highly synchronized dynamic evolution, providing direct experimental evidence for the intrinsic coupling between the optical signal and the electrochemical energy storage state in the electrochromic visualization energy storage window.

[0168] Figure 19 This is a graph showing the output characteristics of the electrochromic organic electrochemical transistor prepared in Example 3 of the present invention. Experimental results show that when the drain-source voltage V is fixed... DS At 0.6V, as the gate-source voltage V... GSAs the voltage increases from -0.8V to 0.15V, the current signal increases from 0.05mA to 0.72mA. This gate voltage-dependent current regulation characteristic provides a key electrical basis for constructing electrochromic visualization organic electrochemical transistors.

[0169] Figure 20 This is a graph showing the output characteristics of the electrochromic organic electrochemical transistor prepared in Comparative Example 3 of this invention. Experimental results show that when the drain-source voltage V is fixed... DS At 0.6V, as the gate-source voltage V... GS As the voltage increased from -0.8V to 0.15V, the current signal increased from 0.02mA to 0.07mA. The amplified signal was much lower than that in Example 3, further confirming the key role of molecular structure design in improving device performance and demonstrating the efficient ion-electron synergistic transport performance of the hybrid ion-electron conductive polymer.

[0170] Figure 21 This is an electrochromic visualization of the electrochromic organic electrochemical transistor prepared in Example 3 of the present invention. This study uses a fixed drain-source voltage Vd. DS At a voltage of 0.6V, the optical transmission characteristics of the electrochromic visual organic electrochemical transistor prepared in Example 3 were systematically characterized using a semiconductor parameter analyzer coupled with a UV-Vis-NIR spectrophotometer under different gate voltages. Experimental results show that as the gate-source voltage V... GS As the wavelength increases, the transmittance of the material at 600 nm decreases from 72.31% to 15.73%. This phenomenon is attributed to the transformation of the tetraaminobiphenyl segment from a reduced state to an oxidized state under electrochemical doping, which leads to enhanced light absorption and decreased transmittance, laying an experimental foundation for the development of visualized organic electrochemical transistors.

[0171] Figure 22 This is a relaxation time distribution diagram of the electrochromic visualization energy storage window prepared in Example 2 of the present invention during the charging and discharging process. -5 ~10 -4 The characteristic peaks in the s-region correspond to the Li⁺ transport process within the polyethylene oxide gel electrolyte / mixed ionic-electron conductive polymer interface film and the electrolyte interface film. -3 The ~1s interval reflects the charge transfer process, while the 1~10s interval is related to the bulk diffusion impedance. This energy storage window exhibits low impedance. This excellent characteristic stems from the good integration between the gel electrolyte and the polymer. Further analysis revealed that this integration benefits from the ethylene glycol segments present in both. The identical ethylene glycol segments provide a continuous and unobstructed channel for ion transport, reducing the resistance to ion migration, thereby effectively reducing the impedance of the energy storage window and improving its charge-discharge performance and overall stability.

[0172] Figure 23The image shows the relaxation time distribution of the electrochromic visualization energy storage window prepared in Comparative Example 4 of this invention during the charging and discharging process. Its relaxation energy density value is greater than that of Example 2. This significant difference strongly highlights the unique advantages of the gel electrolyte in Example 2, indicating that it performs better in promoting ion transport and reducing interfacial resistance, and can effectively improve the overall performance of the electrochromic visualization energy storage window.

[0173] Those skilled in the art will understand that the above-described embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail may be made without departing from the spirit and scope of this application. Any person skilled in the art can make their own modifications and alterations without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A hybrid ion-electron conductive polymer material, characterized in that, Its main chain is both an electronic and ionic conductor, and the polymer has repeating units with the structure shown in formula (I): ； Equation (I) Where n is a positive integer, representing the degree of aggregation.

2. A method for preparing a mixed ion-electron conductive polymer material, characterized in that, Includes the following steps: Step A: Monomer synthesis: A1: Under a nitrogen atmosphere, add 4-hydroxydiphenylamine and sodium hydroxide to a three-necked round-bottom flask containing DMF solvent, and stir mechanically for 1 hour; A2: Add solid potassium iodide to the solution in step A1 above and stir mechanically for 15 minutes; A3: Add diethylene glycol dichloroethyl ester to the solution in step A2 above, and heat and stir for 12 hours; A4: Transfer the mixed solution after the reaction in step A3 to a separatory funnel, and extract the organic layer six times with saturated sodium chloride solution and dichloromethane solution to obtain the organic phase; A5: The organic phase obtained in step A4 is concentrated under reduced pressure and then dried in a vacuum dryer at 60°C to obtain a brown solid. Step B: Synthesis of mixed ionic and electronically conductive polymers: B1: Add the monomer synthesized in step A and p-phenylenediamine to a round-bottom flask containing DMF solvent in sequence, and stir mechanically for 10 minutes. B2: Add 3 mol / L hydrochloric acid solution dropwise to the solution obtained in step B1 under stirring conditions, and stir mechanically until a uniform dispersion is formed; B3: Add solid ammonium persulfate to a 3 mol / L hydrochloric acid solution, and then add the hydrochloric acid solution containing ammonium persulfate dropwise to the dispersion obtained in step B2 under stirring. React at room temperature for 24 hours. B4: After the reaction in step B3 is completed, the mixed solution is transferred to ice water to precipitate, then filtered. The precipitate is then washed successively with distilled water, ethanol and dichloromethane until it is colorless, to obtain the oxidized mixed ionic electronic conductive polymer. B5: Disperse the oxidized mixed ionic conductive polymer obtained in step B4 in an ammonia solution, add hydrazine hydrate for reduction, and then transfer it to a vacuum oven at 45°C to dry for 24 hours to obtain a dark blue solid.

3. The method for preparing a mixed ion-electron conductive polymer material according to claim 2, characterized in that, The molar ratio of 4-hydroxydiphenylamine in step A1 to diethylene glycol dichloroethyl ester in step A3 is 2.5:1; In step B1, the molar ratio of monomer to p-phenylenediamine is 1:1; In step B5, the molar ratio of the oxidized mixed ionic electronic conductive polymer to hydrazine hydrate is 1:

6.

4. The application of a hybrid ion-electron conductive polymer material in an electrochromic visual energy storage window, characterized in that, Includes the following steps: Step 1: Prepare the mixed ion-electro-conducting polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode, and gel electrolyte; Step 2: Assemble the mixed ion-electron conductive polymer / ITO working electrode, vanadium pentoxide / ITO counter electrode and gel electrolyte obtained in Step 1 into a sandwich structure and bond them together with photocurable adhesive. Step 3: Attach the copper strip to the positive and negative poles of the sandwich structure described in Step 2 to obtain the electrochromic visualization energy storage window.

5. The application of the hybrid ion-electron conductive polymer material according to claim 4 in an electrochromic visualization energy storage window, characterized in that, The preparation method of the mixed ion-electron conductive polymer / ITO working electrode described in step one includes the following steps: Step 1: Dissolve the mixed ionic and electronically conductive polymer in DMF solvent to prepare a homogeneous solution; Step 2: Spray the solution obtained in Step 1 onto an ITO glass substrate at 200℃ to obtain a mixed ion-electron conductive polymer / ITO working electrode.

6. The application of the hybrid ion-electron conductive polymer material according to claim 4 in an electrochromic visual energy storage window, characterized in that, The method for preparing the vanadium pentoxide / ITO counter electrode described in step one includes the following steps: Step 1: Dissolve vanadium pentoxide and sodium chloride in deionized water at 60℃, and heat and stir until the color changes from yellow to brown; Step 2: Centrifuge the mixture obtained in Step 1 three times at 6000 r / min, wash with deionized water and ethanol until colorless, and collect the precipitate; Step 3: Transfer the precipitate obtained in Step 2 to a vacuum oven at 45°C and dry for 24 hours to obtain V2O5 nanowires; Step 4: Disperse the V2O5 nanowires described in Step 3 uniformly in deionized water, and then spin-coat the solution onto an ITO glass substrate at a speed of 2000 r / min for 30 seconds to form a uniform thin film. Step 5: Anneal at 60℃ for 1 hour to obtain vanadium pentoxide / ITO counter electrode.

7. The application of a hybrid ionic and electronically conductive polymer material in an electrochromic visualization organic electrochemical transistor, characterized in that, Includes the following steps: Step 1: Dissolve the mixed ionic and electronically conductive polymer in DMF solvent to prepare a homogeneous solution; Step 2: Spray the solution obtained in Step 1 onto the interdigitated gold electrode at 200℃; Step 3: Spin-coat the gel electrolyte onto the interdigitated gold electrode prepared in step 2 to form a uniform thin film. The intersection region of the interdigitated electrode constitutes the source and drain of the transistor.

8. The application according to claim 4 or 7, characterized in that, The preparation of the gel electrolyte includes the following steps: Step 1: Dissolve polyethylene oxide in acetonitrile to prepare a homogeneous solution; Step 2: Add anhydrous propylene carbonate and lithium perchlorate to the solution from Step 1, and stir for 12 hours under a nitrogen atmosphere to obtain a colorless and transparent gel electrolyte.

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