阅读说明：本技术 平面柔性储能变色一体化器件及其制备方法 (Planar flexible energy storage color change integrated device and preparation method thereof ) 是由 胡柳 张亚茹 胡毅 于 2021-08-25 设计创作，主要内容包括：本发明涉及一种平面柔性一体化器件,特别涉及一种平面柔性储能变色一体化器件及其制备方法。本发明通过用高分子聚合物分散电致变色材料获得粘度合适、分散性稳定优异的高性能墨水,采用微电子打印机将其印制在PET等柔性基底上,获得图案化电致变色层；再用类似方法配制导电电极墨水,并在电致变色层上部二次精准打印导电电极层；最后,在电致变色层图案上部印制凝胶电解质,并将两部分电致变色层组装获得完整平面柔性储能变色一体化器件。本发明通过微电子打印技术的应用、高性能墨水的制备、柔性基材、电致变色及导电电极材料的筛选等实现了平面化柔性电容储能电致变色一体化器件机械柔性、光学性能和电化学性能的全方位提升。(The invention relates to a planar flexible integrated device, in particular to a planar flexible energy storage and color change integrated device and a preparation method thereof. The invention obtains high-performance ink with proper viscosity and stable and excellent dispersibility by dispersing the electrochromic material with high molecular polymer, and the high-performance ink is printed on flexible substrates such as PET and the like by adopting a microelectronic printer to obtain a patterned electrochromic layer; preparing conductive electrode ink by a similar method, and accurately printing a conductive electrode layer on the upper part of the electrochromic layer for the second time; and finally, printing gel electrolyte on the upper part of the pattern of the electrochromic layer, and assembling the two parts of the electrochromic layer to obtain the complete planar flexible energy storage and color change integrated device. The invention realizes the comprehensive improvement of mechanical flexibility, optical performance and electrochemical performance of the planar flexible capacitance energy storage electrochromic integrated device by applying a microelectronic printing technology, preparing high-performance ink, screening flexible base materials, electrochromic and conductive electrode materials and the like.)

1. A preparation method of a planar flexible energy storage and color change integrated device comprises a flexible substrate, an electrochromic layer, an electrolyte layer and a conductive electrode layer, and is characterized by comprising the following steps:

(1) ink preparation of electrochromic and conductive electrode layers

Dispersing an electrochromic material in a solvent by using a high-viscosity organic high-molecular polymer, adjusting the viscosity of the ink to 20-100mPa & s, and stirring to obtain the electrochromic ink with good dispersion stability for printing;

dispersing the conductive electrode material by using a solvent, adjusting the viscosity to 20-100mPa & s by using a high-conductivity polymer, and stirring to obtain conductive electrode layer ink for printing an electrochromic device;

(2) patterned electrochromic layer and conductive electrode layer

Under the assistance of drawing software, a printer is adopted to design and draw patterns according to the requirements of the energy storage and color change integrated device, parameters are set through an adjusting system, pattern printing is carried out on the flexible base material, a conductive electrode layer is obtained, and drying is carried out;

continuously printing an electrochromic layer on the conductive electrode layer by using electrochromic ink by adopting the microelectronic printing method, and drying;

(3) printing gel electrolyte on the pattern of the electrochromic layer, assembling the two electrochromic layers together, and sealing and packaging to obtain the planar flexible energy storage and color change integrated device.

2. The method of claim 1, wherein: the electrochromic material in the step (1) is WO₃、TiO₂、MoO₃Polypyrrole and polyanilineOne or more of polythiophene, Prussian blue, heteropoly acid or metal phthalocyanine compound.

3. The method of claim 1, wherein: the organic high molecular polymer in the step (1) is selected from one or more of polyvinylpyrrolidone (PVP), waterborne Polyurethane (PU), polyethylene oxide (PEO), polyacrylamide (CPAM), Hydrolyzed Polyacrylamide (HPAM), carboxymethyl starch, starch acetate, hydroxymethyl cellulose, carboxymethyl cellulose (CMC) or sodium alginate.

4. The method of claim 1, wherein: the conductive electrode material in the step (1) is selected from one or more of silver nanowires (Ag NWs), Carbon Nanotubes (CNTs), graphene, Mxene or PEDOT and PSS.

5. The method of claim 1, wherein: the solvent in the step (1) is selected from one or more of ethanol, Isopropanol (IPA), deionized water, N Dimethylformamide (DMF), N Methyl Pyrrolidone (NMP), propylene carbonate or ethyl acetate; the high-conductivity polymer is polypyrrole, polyaniline or polythiophene.

6. The method of claim 1, wherein: the viscosity of the electrochromic ink is 20-50 mPa.s, and the viscosity of the conductive electrode ink is 40-60 mPa.s.

7. The method of claim 1, wherein: the flexible substrate in the step (2) is polyethylene terephthalate (PET), Polydimethylsiloxane (PDMS) film, polymethyl methacrylate (PMMA) or styrene-butadiene-styrene block copolymer (SBS).

8. The method of claim 1, wherein: adjusting the system parameters in the step (2) according to the size, line thickness, fineness, resolution and the like of the printed pattern; the drying condition is 80-120 deg.C, 5-60 min.

9. The method of claim 1, wherein: the gel electrolyte in the step (2) is PVA/KOH or PVA/H₂SO₄、CMC/NaSO₄、PVA/LiCl、LiClO₄PMMA/PC or potassium hexafluorophosphate (KPF)₆) PMMA/propylene carbonate (C)₄H₆O₃) Ethyl acetate (C)₄H₈O₂)。

10. The planar flexible energy storage color change integrated device prepared by the preparation method of claim 1.

Technical Field

The invention relates to a planar flexible integrated device, in particular to a planar flexible energy storage color change integrated device and a preparation method thereof, and belongs to the technical field of energy storage devices.

Background

With the rapid development of economy and the continuous increase of energy consumption, the energy crisis has become one of the biggest problems in the current society, and the intelligent management of energy consumption has become a method for solving the energy problem. The energy storage color changing device is a typical multifunctional device integrating color changing and energy storage functions, has the characteristics of low working voltage, multiple stable states, static state without power consumption, continuously adjustable transmittance, long service life, low cost and the like, can judge the power supply energy consumption condition through vision, and provides a method for intelligently managing energy consumption. The intelligent energy-saving window has wide application in the fields of intelligent energy-saving windows, low-energy consumption displays, automobile anti-dazzling rearview mirrors, electronic books, intelligent glasses, infrared stealth, satellite thermal control and the like.

In recent years, the structural design and operation principle of such multifunctional devices have been continuously studied, but still need to be improved. From the electrochemical principle, the electrochromic device, a battery and a super capacitor have the same structure, and both electrochromic and energy storage processes are originated from electrochemical redox reaction, and the electrochemical redox reaction process is closely related to the surface area and the conductivity of an active material. Therefore, by further fusing the electrochromic technology and the energy storage device technology, the device structure can be optimized, and a high-performance planar flexible energy storage and color change integrated device can be developed. In addition, the development of a novel electrochromic active material with high surface area and high conductivity is very important for improving the performance of the energy storage and color change integrated device. For electrochromic devices, ideal electrode materials require not only high conductivity but also excellent light transmittance, chemical resistance, and electrochemical corrosion resistance. And the conductivity of the conventional ITO electrochromic electrode material is not enough to obtain high response speed. Under low strain, the ITO thin film is also easy to crack, so that the conductivity of the ITO thin film is reduced rapidly, and the performance of the whole device is influenced. Therefore, how to overcome the brittleness of the conductive film is a technical bottleneck in the field to improve the conductivity and the flexibility. In addition, indium element is scarce and precious, and finding other conductive materials to replace the traditional ITO also becomes a current research hotspot.

In recent years, nano conductive materials such as: metal nanomaterials (such as metal nanowires and metal grids), carbon materials (such as carbon nanotubes and graphene), and nano-doped metal oxides are widely studied. The nanometer conductive materials can be used for electrochromic devices, so that the electrochromic performance can be improved, and the development of next-generation multifunctional and flexible wearable devices can be promoted. Common nano conductive materials in electrochromic devices include silver nanowires, carbon nanotubes, graphene, nano-doped metal oxides and mixed conductive nanomaterials. The development and application of the materials not only realize the improvement of the optical performance and the electrochemical performance of the electrochromic nano film and the device, but also promote the improvement of the mechanical flexibility of the device.

In addition, the key of the preparation of the electrochromic energy device lies in the preparation of the electrochromic electrode, particularly the design of the patterned electrode, the traditional processes of physical deposition, spray mask and the like are complex, the efficiency is low, and the development of the electrochromic energy device is severely limited. In order to solve the above problems, many researches have been made thereon. The printing technology has mature technology, wide application range, low cost, good reliability and high yield, and is very suitable for the macro-quantitative preparation of the planar device. It can be obtained by printing the functional material in an ink with proper rheological property. As a new intelligent manufacturing technology, the method can realize integration while realizing large-scale preparation so as to improve the overall performance of the device. The electrochromic functional material is prepared into stable ink, and the patterned electrode is prepared in a printing mode, so that a reliable and efficient new scheme is provided for the preparation of an electrochromic energy device. Therefore, the synthetic preparation of the high-performance ink has important significance for expanding the application of efficient printing technology to the preparation of flexible functional devices.

Disclosure of Invention

The invention provides a planar flexible energy storage and color change integrated device, which has the advantages that the mechanical flexibility, the optical performance and the electrochemical performance are improved in an all-round way.

The invention also provides a preparation method of the planar flexible energy storage color change integrated device, which is simple and convenient, can easily realize integration while endowing the device with planarity and flexibility, endows the energy storage color change device with excellent electrochemical and optical properties, and provides a new research direction and thought for low-cost preparation of the integrated device.

The technical scheme adopted by the invention for solving the technical problems is as follows:

a preparation method of a planar flexible energy storage and color change integrated device comprises a flexible substrate, an electrochromic layer, an electrolyte layer and a conductive electrode layer, and comprises the following steps:

(1) ink preparation of electrochromic and conductive electrode layers

Dispersing an electrochromic material in a solvent by using a high-viscosity organic high-molecular polymer, adjusting the viscosity of the ink to be 20-100mPa & s (preferably 20-50mPa & s), and stirring to obtain the electrochromic ink with good dispersion stability for printing;

after the conductive electrode material is dispersed by a solvent, the viscosity is adjusted to 20-100mPa & s (preferably 40-60mPa & s) by using a high-conductivity polymer, and the conductive electrode layer ink for printing an electrochromic device is obtained after stirring;

(2) patterned electrochromic layer and conductive electrode layer

Under the assistance of drawing software, a printer (matched with the drawing software) is adopted to design and draw patterns according to the requirements of the energy storage and color change integrated device, parameters (the size, the height and the position of a needle head, printing air pressure and printing times) are set through an adjusting system, pattern printing is carried out on a flexible substrate, a conductive electrode layer is obtained, and drying is carried out;

continuously printing an electrochromic layer on the conductive electrode layer by using electrochromic ink by adopting the microelectronic printing method, and drying;

(3) printing gel electrolyte on the pattern of the electrochromic layer, assembling the two electrochromic layers together, and sealing and packaging to obtain the planar flexible energy storage and color change integrated device.

The preparation method is simple and flexible, is easy to expand, can be used for small-batch and multi-style production, and has beautiful and diversified patterns; the prepared printing ink has excellent performance and good dispersion stability; the prepared planar flexible energy storage and color change integrated device not only maintains excellent energy storage performance, but also realizes optical performance (electrochromic performance), and simultaneously endows the device with excellent mechanical flexibility, thereby having important significance for the expansibility development and production of flexible and wearable electronic equipment.

Preferably, the viscosity of the electrochromic ink is 20 to 50 mPas, and the viscosity of the conductive electrode ink is 40 to 60 mPas. Through the size, height, position, printing atmospheric pressure and the number of times of printing of accurate regulation printer syringe needle, ensure the higher definition and the resolution ratio of printed pattern, do benefit to the accurate register of secondary to guarantee the realization of the excellent electrochemistry performance of device and optical property.

Preferably, the electrochromic material is WO₃、TiO₂、MoO₃One or more of polypyrrole, polyaniline, polythiophene, Prussian blue, heteropoly acid or metal phthalocyanine compounds.

Preferably, the organic high molecular polymer in step (1) is selected from one or more of polyvinylpyrrolidone (PVP), aqueous Polyurethane (PU), polyethylene oxide (PEO), polyacrylamide (CPAM), Hydrolyzed Polyacrylamide (HPAM), carboxymethyl starch, starch acetate, hydroxymethyl cellulose, carboxymethyl cellulose (CMC) or sodium alginate.

Preferably, the conductive electrode material in step (1) is selected from silver nanowires, Carbon Nanotubes (CNTs), graphene, Mxene or PEDOT: one or more of PSS.

Preferably, the solvent is one or more selected from ethanol, Isopropanol (IPA), deionized water, N Dimethylformamide (DMF), N Methyl Pyrrolidone (NMP), propylene carbonate or ethyl acetate; the high-conductivity polymer is polypyrrole, polyaniline or polythiophene.

Preferably, the microelectronic printer (provided with Bits Assembler drawing software) in the step (2) can be used for printing, and the printers for printing can be an MP1100 microelectronic printer, an MF3D-200 type 3D hybrid printer and a DB100 printing electronic multifunctional 3D printer.

Preferably, the flexible substrate in step (2) may be polyethylene terephthalate (PET), Polydimethylsiloxane (PDMS) film, Polymethylmethacrylate (PMMA), or styrene-butadiene-styrene block copolymer (SBS).

Preferably, the system parameters in step (2) are adjusted according to the size of the printing pattern, the thickness of lines, the fineness, the resolution and the like; the drying condition is 80-120 deg.C, 5-60 min.

Preferably, the gel electrolyte in step (3) is KOH/PVA, KOH/H₂SO₄、CMC/NaSO₄、KOH/LiCl、LiClO₄PMMA/PG or potassium hexafluorophosphate (KPF)₆) PMMA/propylene carbonate (C)₄H₆O₃) Ethyl acetate (C)₄H₈O₂)。

The planar flexible energy storage color change integrated device prepared by the preparation method has excellent mechanical flexibility, electrochemical performance and optical performance.

Firstly, dispersing an electrochromic material by using a high molecular polymer to obtain printing ink with proper viscosity and stable and excellent dispersibility, and printing the printing ink on a flexible substrate by using a microelectronic printer to obtain a patterned electrochromic layer; preparing conductive electrode ink and secondarily and accurately printing a conductive electrode layer by the same method; and finally, printing gel electrolyte on the pattern of the electrochromic layer, and assembling the two electrochromic layers to obtain the complete planar flexible energy storage and color change integrated device. The preparation method can be expanded to be applied to the field of flexible and wearable energy storage devices, and compared with the prior art, the preparation method has the following characteristics:

1. the invention uses the microelectronic printing technology, has simple operation steps, convenient and fast integration and is suitable for industrial production;

2. the prepared electrochromic ink and the prepared conductive electrode ink have good dispersion stability and viscosity, and can be well matched with microelectronic printing technology;

3. the prepared planar flexible energy storage color change integrated device has excellent mechanical flexibility, electrochemical performance and optical performance, and simultaneously realizes energy storage and electrochromism, thereby embodying the design concept of intelligent batteries.

Drawings

FIG. 1 is a constant current charge and discharge (GCD) curve of a planar flexible zinc ion capacitor energy storage electrochromic integrated device obtained in example 1 under different current densities;

fig. 2 is a current-voltage (CV) curve of different scanning rate systems of the planar flexible graphene capacitive energy storage electrochromic integrated device obtained in example 2;

fig. 3 is an Electrochemical Impedance Spectrum (EIS) of the planar flexible graphene capacitive energy storage electrochromic integrated device obtained in example 2;

FIG. 4 is a constant current charge and discharge (GCD) curve of the planar flexible Mxene capacitive energy storage electrochromic integrated device obtained in example 3 under different current densities;

FIG. 5 is a current-voltage (CV) curve of different scanning rate systems of the planar flexible carbon nanotube capacitive energy storage electrochromic integrated device obtained in example 4;

figure 6 is the resulting planar flexible PEDOT of example 5: and (3) an Electrochemical Impedance Spectrum (EIS) of the PSS capacitive energy storage electrochromic integrated device.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.

In the invention, all parts and percentages are weight units, and all equipment, raw materials and the like can be purchased from the market or are commonly used in the industry, if not specified.

Example 1

A preparation method of a planar flexible zinc ion capacitor energy storage electrochromic integrated device comprises the following specific steps:

(1) electrochromic layer and conductive electrode ink preparation

Dispersing nano tungsten trioxide in NMP by polyvinylpyrrolidone (PVP)(WO₃) Adjusting the viscosity of the ink to 42mPa & s, and stirring at the rotating speed of 1000r/min for 10min to obtain the WO with good dispersion stability for microelectronic printing₃An electrochromic ink;

dispersing Ag NWs and nano zinc powder by using ethanol, adjusting the viscosity to about 50mPa & s by using polypyrrole, stirring at the rotating speed of 1000r/min for 5min, and stirring to obtain Ag NWs/Zn conductive electrode ink for printing;

the electrochromic ink comprises the following components in percentage by weight: nano tungsten trioxide (WO)₃)10 percent, 5 percent of polyvinylpyrrolidone (PVP) and the balance of NMP, wherein the total weight of the ink is 100 percent.

The conductive electrode ink comprises the following components in percentage by weight: 7.5 percent of Ag NWs, 10 percent of nano zinc powder, 2.5 percent of polypyrrole and the balance of ethanol, wherein the total weight of the ink is 100 percent.

(2) Patterned electrochromic layer and conductive electrode layer

Adopting the ink prepared in the step (1), designing and drawing a pattern of a school badge symmetric device under the assistance of drawing software, and printing on an ozone-treated PET film by adjusting system setting parameters (the aperture of a needle head is 250 mu m, the height is 100 mu m, the speed is 2mm/s, the air pressure is 240kPa and printing is carried out for 1 time) to obtain an Ag NWs/Zn conductive electrode layer; after printing, drying at 80 ℃ for 10 min.

Adjusting the position to the same position of the symmetrical pattern (air pressure 250kPa, needle height 200 μm) by the same method, and printing WO on the conductive electrode layer pattern₃The ink yielded an electrochromic layer. Finally, drying for 10min at 100 ℃.

(3) In oven dried WO₃And further printing 6M PVA/KOH gel electrolyte (the diameter of a needle is 250 mu M, the height is 300 mu M, the speed is 3mm/s, and the air pressure is 200kPa) on the pattern of the electrochromic layer, and assembling the obtained electrochromic layer with two parts covering the gel electrolyte together to obtain the planar flexible zinc ion capacitance energy storage electrochromic integrated device.

Supplementary example 1: preparation of gel electrolyte

PVA/KOH gel electrolyte: 6.72g of KOH was dissolved in 20mL of deionized water, 6g of PVA was added to the above solution, and the mixture was heated in an oil bath at 85 ℃ with stirring until a uniform mixture was obtained.

PVA/LiCl gel electrolyte: 1.70g LiCl is added into 20mL deionized water and stirred until dissolved, then 2g PVA is added, and the mixture is heated and stirred in an oil bath at 95 ℃ until completely uniform.

CMC/NaSO₄Gel electrolyte: 20mL DI was charged with 3g CMC and 2g Na₂SO₄The gel was stirred in an oil bath at 85 ℃ for 3h until it was clear.

PVA/H₂SO₄Gel electrolyte: slowly adding 2.5g of concentrated sulfuric acid into 20mL of DI water, adding 2.5g of CMC powder, heating and stirring at 85 ℃ for 2h until the CMC is uniformly dispersed and transparent, and cooling to room temperature.

PVA/LiCl gel electrolyte: dissolving 4g LiCl in deionized water, adding 2g PVA, stirring in an oil bath at 95 ℃ until the gel becomes clear and transparent, and finally cooling to room temperature.

LiClO₄PMMA/PC electrolyte: LiClO4(0.5mol/L) and PMMA (35 wt%) were dissolved in PC to give a homogeneous viscous solution.

Example 2

A preparation method of a planar flexible graphene capacitive energy storage electrochromic integrated device comprises the following specific steps:

(1) electrochromic layer and conductive electrode ink preparation

Dispersing molybdenum trioxide (MoO) in ethanol solution with polyethylene oxide (PEO)₃) Adjusting the viscosity of the ink to about 38mPa & s, and stirring at the rotating speed of 800r/min for 15min to obtain MoO with good dispersion stability for microelectronic printing₃An electrochromic ink;

dispersing polyaniline and reduced graphene oxide (rGO) by using ethanol, stirring at the rotating speed of 1000r/min for 15min, and stirring to obtain polyaniline/rGO conductive electrode ink with the viscosity of about 40mPa & s, which can be used for microelectronic printing;

the electrochromic ink formula comprises: nano molybdenum trioxide (MoO)₃)12 percent, 4 percent of polyethylene oxide (PEO) and the balance of ethanol, wherein the total weight of the ink is 100 percent.

The conductive electrode ink formula comprises: 5% of polyaniline, 12% of reduced graphene oxide (rGO) and the balance of ethanol, wherein the total weight of the ink is 100%.

(2) Patterned electrochromic layer and conductive electrode layer

Adopting the printing ink prepared in the step (1), designing and drawing a pattern of a school badge symmetric device under the assistance of drawing software, and printing on a self-made PDMS membrane by adjusting system setting parameters (the aperture of a needle head is 250 mu m, the height is 150 mu m, the speed is 1.5mm/s, the air pressure is 200kPa and printing is carried out for 1 time) to obtain a polyaniline/rGO conductive electrode layer; after printing, drying at 100 ℃ for 10 min. Then, the same method is adopted, the position is adjusted to the same position (the air pressure is 220kPa, the needle position is 250 mu m), and MoO is printed on the conductive electrode layer pattern₃The ink yielded an electrochromic layer. Finally, drying for 10min at 100 ℃.

(3) In the dried MoO₃And further printing PVA/LiCl gel electrolyte (the aperture of a needle is 250 mu m, the height of the needle is 350 mu m, the speed of the needle is 3mm/s, and the air pressure of the needle is 220kPa) on the pattern of the electrochromic layer, and assembling the obtained two electrochromic layers with the gel electrolyte covered on the two parts together to obtain the planar flexible graphene capacitance energy storage electrochromic integrated device.

Supplementary example 2: PDMS Membrane preparation

SYGARD184 silicone elastomer matrix and 184 silicone elastomer matrix curing agent in a weight ratio of 10: 1, mixing and stirring for 30-60min, coating on a PTFE film, curing for 30min at 120 ℃, and tearing off the PTFE film for later use.

Example 3

A preparation method of a planar flexible Mxene capacitive energy storage electrochromic integrated device comprises the following specific steps:

(1) electrochromic layer and conductive electrode ink preparation

Dispersing nanometer titanium dioxide (TiO) in water and isopropanol mixed solution (5: 1) by using polyacrylamide (CPAM)₂) Adjusting the viscosity of the printing ink to about 32mPa & s, and stirring at the rotating speed of 1000r/min for 12min to obtain TiO with good dispersion stability for microelectronic printing₂An electrochromic ink;

after polyaniline and Mxene are dispersed by a mixed solution (5: 1) of water and isopropanol, stirring at the rotating speed of 1000r/min for 12min to obtain polyaniline/Mxene conductive electrode ink with the viscosity of about 45mPa & s and capable of being used for microelectronic printing;

the electrochromic ink formula comprises: nano titanium dioxide (TiO)₂) 10%, Polyaniline (PEO) 5%, and the balance being a mixed solution of water and isopropyl alcohol (5: 1) the total weight of the ink is 100 percent.

The conductive electrode ink formula comprises: 5% of polyaniline, 15% of Mxene and the balance of a mixed solution (5: 1) of water and isopropanol, wherein the total weight of the ink is 100%.

(2) Patterned electrochromic layer and conductive electrode layer

Adopting the printing ink prepared in the step (1), designing and drawing a pattern of a school badge symmetric device under the assistance of drawing software, and printing on a self-made SBS elastic film by adjusting system setting parameters (the aperture of a needle head is 250 mu m, the height is 100 mu m, the speed is 2mm/s, the air pressure is 220kPa and printing is carried out for 1 time) to obtain a polyaniline/Mxene conductive electrode layer; after printing, drying at 80 ℃ for 10 min. Then, the same method is adopted, the position is adjusted to the same position (the air pressure is 250kPa, the needle position is 200 mu m), and TiO is printed on the conductive electrode layer pattern₂The ink yielded an electrochromic layer. Finally, drying for 10min at 100 ℃.

(3) In the presence of dried TiO₂The pattern of the electrochromic layer is further printed with CMC/NaSO₄Gel electrolyte (the aperture of a needle is 250 mu m, the height is 300 mu m, the speed is 3mm/s, the air pressure is 250kPa), and the obtained two electrochromic layers with the gel electrolyte covered on the two parts are assembled together, so that the planar flexible Mxene capacitive energy storage electrochromic integrated device is obtained.

Supplementary example 2: preparation of SBS elastic film

Styrene-butadiene-styrene block copolymer (SBS) and toluene in a weight ratio of 1: mixing and stirring for 1-5h at 80 ℃ in 4 oil bath, coating on the PTFE film, curing for 30min at room temperature, and tearing off the PTFE film for later use.

Example 4

A method for preparing a planar flexible carbon nanotube capacitive energy storage electrochromic integrated device comprises the following specific steps:

(1) electrochromic layer and conductive electrode ink preparation

Using Hydrolyzed Polyacrylamide (HPAM) in ethanol solutionMiddle dispersed molybdenum trioxide (MoO)₃) Adjusting the viscosity of the ink to about 40mPa & s, and stirring at the rotating speed of 1000r/min for 15min to obtain MoO with good dispersion stability for microelectronic printing₃An electrochromic ink;

dispersing polythiophene and multi-walled Carbon Nanotubes (CNTs) by using a mixed solution of water and ethanol, stirring at the rotating speed of 1000r/min for 15min, and stirring to obtain polythiophene/CNTs conductive electrode ink with the viscosity of about 45 mPas and capable of being used for microelectronic printing;

the electrochromic ink formula comprises: nano molybdenum trioxide (MoO)₃)12 percent of polythiophene, 8 percent of polythiophene and the balance of a mixed solution of water and ethanol, wherein the total weight of the ink is 100 percent.

The conductive electrode ink formula comprises: 6% of polythiophene, 14% of CNTs and the balance of a mixed solution of water and ethanol, wherein the total weight of the ink is 100%.

(2) Patterned electrochromic layer and conductive electrode layer

Adopting the ink prepared in the step (1), designing and drawing a pattern of a school badge symmetric device under the assistance of drawing software, and printing on a PET film by adjusting system setting parameters (the aperture of a needle head is 250 mu m, the height is 100 mu m, the speed is 1.5mm/s, the air pressure is 250kPa and printing is carried out for 1 time) to obtain a polythiophene/CNTs conductive electrode layer; after printing, drying at 100 ℃ for 10 min. Then, the same method is adopted, the position is adjusted to the same position (the air pressure is 220kPa, the needle position is 200 mu m), and MoO is printed on the conductive electrode layer pattern₃The ink yielded an electrochromic layer. Finally, drying for 10min at 100 ℃.

(3) In the dried MoO₃PVA/H is further printed on the pattern of the electrochromic layer₂SO₄Gel electrolyte (the aperture of the needle is 300 mu m, the height is 300 mu m, the speed is 2mm/s, the air pressure is 250kPa), and the obtained two electrochromic layers with the gel electrolyte covered on the two parts are assembled together, so that the planar flexible carbon nanotube capacitive energy storage electrochromic integrated device is obtained.

Example 5

A planar flexible PEDOT: the preparation method of the PSS capacitive energy storage electrochromic integrated device comprises the following specific steps:

(1) electrochromic layer and conductive electrode ink preparation

Dispersing Prussian blue in an aqueous solution by using sodium alginate, adjusting the viscosity of the ink to be about 48mPa & s, and stirring at the rotating speed of 800r/min for 15min to obtain Prussian blue electrochromic ink with good dispersion stability for microelectronic printing;

mixing polyaniline and 3, 4-ethylenedioxythiophene: dispersing polystyrene sulfonic acid (PEDOT: PSS) by using a water mixed solution, stirring at the rotating speed of 800r/min for 15min to obtain polyaniline/PEDOT: PSS conductive electrode ink;

the electrochromic ink formula comprises: 14% of Prussian blue, 6% of sodium alginate and the balance of deionized water, wherein the total weight of the ink is 100%.

The conductive electrode ink formula comprises: polyaniline 8%, PEDOT: PSS 12%, and the balance being deionized water, wherein the total weight of the ink is 100%.

(2) Patterned electrochromic layer and conductive electrode layer

Adopting the ink prepared in the step (1), designing and drawing a school badge symmetric device pattern under the assistance of drawing software, and printing on a self-made PDMS film by adjusting system setting parameters (the aperture of a needle is 250 mu m, the height is 150 mu m, the speed is 3mm/s, the air pressure is 200kPa and printing is carried out for 1 time) to obtain polyaniline/PEDOT: a PSS conductive electrode layer; after printing, drying at 80 ℃ for 10 min. Then, the same method was used, the pressure was adjusted to the same position (air pressure 220kPa, needle position 250 μm), and Prussian blue ink was printed on the above-mentioned conductive electrode layer pattern to obtain an electrochromic layer. Finally, drying for 10min at 80 ℃.

(3) Further printing LiClO on the dried Prussian blue electrochromic layer pattern₄PMMA/PC electrolyte (needle aperture 300 μm, height 350 μm, speed 2mm/s, gas pressure 300kPa), and the resulting two part gel electrolyte covered electrochromic layers were assembled together, i.e. a planar flexible PEDOT: PSS electric capacity energy storage electrochromic integrated device.

Analysis of test results

Fig. 1 is a constant current charge and discharge (GCD) curve of the planar flexible zinc ion capacitive energy storage electrochromic integrated device obtained in example 1 under different current densities, and it can be seen that zinc is used as a capacitive energy storage material, which not only has a faster charge and discharge speed and can meet the requirement of fast response of the electrochromic device, but also has a good pseudocapacitance characteristic, indicating that the planar flexible zinc ion capacitive energy storage electrochromic integrated device is a typical planar flexible zinc ion capacitive energy storage electrochromic integrated device.

FIG. 2 is a current-voltage (CV) curve of the planar flexible graphene integrated capacitive energy storage electrochromic device obtained in example 2 in different scanning rate systems, ranging from 5 mVs to 100mVs^-1CV curves under different scanning rates show a similar rectangular shape, which shows that the graphene electrode has obvious double-layer capacitance characteristics, and along with the increase of the scanning rate, the area of the similar rectangular shape is increased, the area capacitance of the device is highlighted, and the side surface shows that the performance of the electrochromic performance under different current voltages is kept good.

Fig. 3 is an Electrochemical Impedance Spectrum (EIS) of the planar flexible graphene capacitive energy storage electrochromic integrated device obtained in example 2, wherein a high-frequency region of an EIS curve shows a small alternating current series resistance (< 500 Ω, z-axis intercept) and a small charge transfer resistance (incomplete semi-circle diameter) of the device, which illustrates excellent ion diffusion kinetics; the slope of the low-frequency tail part shows that the whole device has better conductivity, and the conductivity of the prepared ink is proved to be excellent. The performance is favorable for improving the coloring time and the fading time of electrochromism, and the overall performance of the energy storage and color change integrated device is favorably improved.

FIG. 4 shows that the planar flexible Mxene capacitive energy storage electrochromic integrated device obtained in example 3 is 25-125 μ Acm^-2Constant current charge-discharge (GCD) curves at different current densities prove the fast response characteristic and relatively good multiplying power characteristic of the device. The triangular shape of the material shows the excellent electrochemical energy storage and electronic conductivity of the Mxene pseudocapacitance material, and also proves the excellent energy storage color changing performance of the device.

FIG. 5 shows the integrated planar flexible carbon nanotube integrated capacitive energy storage electrochromic device of 5-100mVs obtained in example 4^-1The current-voltage (CV) curve under different scanning rates is similar to that of graphene, the carbon nano tube is used as a double electric layer capacitor material, and the carbon nano tube capacitor energy storage is electrically changedThe color shows a quasi-rectangular shape and has better area capacitance.

FIG. 6 is an Electrochemical Impedance Spectroscopy (EIS) of the planar flexible PEDOT/PSS integrated capacitive energy storage electrochromic device obtained in example 5, which confirms that the ink prepared from the PEDOT/PSS material has excellent conductivity, shows excellent redox characteristics in an electrochromic process, has high color change response speed, and is very suitable for preparing the integrated capacitive energy storage electrochromic device.

The method for preparing the planar flexible energy storage electrochromic integrated device by adopting the microelectronic printing technology is simple, large-scale production can be realized, the preparation method is flexible, and the preparation of small-batch and multi-variety planar flexible energy storage electrochromic integrated devices can be met. The prepared planar flexible energy storage color change integrated device is excellent in electrochemical performance, mechanical flexibility and optical performance. Compared with the current single miniature super capacitor and electrochromic device, the flexible electronic device has relatively better performance, meets the requirements of the current integrated device in the flexible electronic field, and promotes the development of the flexible electronic device. According to the invention, the comprehensive improvement of mechanical flexibility, optical performance and electrochemical performance of the planar flexible capacitance energy storage electrochromic integrated device is realized through the application of a microelectronic printing technology, the preparation of high-performance ink, the screening of a flexible substrate, electrochromic and conductive electrode materials and the like, and the planar flexible capacitance energy storage electrochromic integrated device has important significance on the expansibility development of flexible and wearable electronic equipment and the intelligent management of energy consumption.

The embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same or similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.

The planar flexible energy storage color change integrated device and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.