CN113421778B - Flexible micro super capacitor and manufacturing method thereof - Google Patents
Flexible micro super capacitor and manufacturing method thereof Download PDFInfo
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a flexible micro super capacitor and a manufacturing method thereof, comprising the following steps: manufacturing a flexible substrate on a substrate; printing a female die by adopting an electric field driven jet deposition micro-nano 3D printing technology; depositing an electrode material on the master mold through an electrochemical polymerization process; uniformly coating a solid electrolyte on an electrode material; and sealing and manufacturing the flexible micro super capacitor. The low-cost batch manufacturing of the conductive high-molecular flexible miniature super capacitor is realized by combining the electric field driven jet deposition micro-nano 3D printing and electrochemical polymerization technology.
Description
Technical Field
The application belongs to the field of 3D printing and energy, and particularly relates to a flexible micro supercapacitor and a manufacturing method thereof.
Background
In the rapid development of miniaturized, portable and highly integrated flexible electronics, the demand for miniature flexible power supplies and energy storage units is increasing. The micro-nano-micro-electro-mechanical system is widely applied to multiple fields of portable wireless communication systems, micro-electro-mechanical systems, biological wireless sensors, multifunctional micro/nano systems, micro robots, wearable/implantable medical equipment and the like. Micro batteries are the main choice for manufacturing micro power supply systems, however, due to their disadvantages of low power density and short cycle life, they greatly limit their widespread use in microelectronic devices, particularly in implantable electro-medical devices. Therefore, new, miniature devices with efficient energy storage are in need of development.
In recent years, flexible Micro Supercapacitors (MSCs) have attracted particular attention in various fields because of their advantages of high power density, excellent cycle life and fast charge/discharge rate, good mechanical properties, etc., which have become desirable alternatives to micro batteries. Traditionally, microelectronic devices are powered by MSCs made of vertical sandwich structures, but easily result in short-circuiting of the top and bottom electrodes. To prevent device failure due to short circuits, the two electrodes must be filled with a sufficiently thick active material to ensure the necessary distance separation. However, this also increases the ion transport resistance, thereby reducing the power density of the device. In addition, since the vertical sandwich structure makes the MSC have a high thickness, it is difficult to integrate into the microelectronic device. In contrast, the in-plane MSC with finger electrodes is based on an interdigitated structure, characterized in that the finger electrodes and the current collectors are in the same plane and isolated from each other by insulating gaps, which is more suitable for integrated circuits. Due to the unique characteristics of high conductivity, a rapid charge/discharge mechanism, good thermal stability and flexibility, low cost, high energy density and the like, the high-molecular conductive polymer becomes a commonly used electrode material in the field of supercapacitors. However, even with these advantages, challenges still remain, the main ones of which are: first, it is necessary to develop a high resolution interdigital pattern fabrication technology, and to assemble an electrode material on a wearable flexible plate so that it can be attached to a small fixed area (maximum size: 1 cm) 2 ) Are integrated with other flexible electronic components. Secondly, the conductive polymer is difficult to be made into an interdigital structure, and is often mixed with other materials for forming, so that the electrochemical performance of the conductive polymer is greatly reduced. Thirdly, an interdigital structure with a large height-width ratio needs to be manufactured, so that the contact area between an electrode material and an electrolyte is larger, and the capacitance of the MSC is greatly improved in an effective unit area.
The current manufacturing process of the interdigital flexible MSC is very limited, such as photolithography, plasma etching, laser scribing and inkjet printing methods. Although these conventional microfabrication methods have been successfully used in the fabrication of micro devices, their process flow is not easily integrated into specific flexible and wearable substrates, and most are only suitable for the preparation of interdigital electrodes with specific materials, with low aspect ratio of the interdigital structure; some manufacturing processes require expensive facilities, expensive chemicals, clean rooms, high environmental requirements, complex manufacturing processes, low efficiency, and generate a lot of waste material and pollution. The existing technologies or solutions have defects and limitations in the aspects of miniature, flexible, efficient, low-cost and mass manufacturing, seriously affect and restrict the wider commercial application of the interdigital miniature flexible supercapacitor, and a new manufacturing method and strategy are urgently needed to be developed so as to realize the efficient, low-cost and large-scale manufacturing of the conductive polymer-based interdigital miniature flexible supercapacitor.
Disclosure of Invention
In order to solve the problems, the application provides a flexible micro supercapacitor and a manufacturing method thereof, and the low-cost batch manufacturing of the conductive high-molecular flexible micro supercapacitor is realized by combining an electric field driven jet deposition micro-nano 3D printing technology and an electrochemical polymerization technology.
In order to achieve the above purpose, in some embodiments of the present application, the following technical solutions are adopted:
a manufacturing method of a flexible miniature super capacitor comprises the following steps:
(1) Manufacturing a flexible substrate on a substrate;
(2) Printing a female die by adopting an electric field driven jet deposition micro-nano 3D printing technology;
(3) Depositing an electrode material on the master die through an electrochemical polymerization process;
(4) Uniformly coating a solid electrolyte on an electrode material;
(5) And sealing and manufacturing the flexible miniature super capacitor.
In some embodiments of the present application, in the step (1), the substrate is cleaned and dried, and the plasma bombardment treatment is performed on the surface of the substrate using a plasma treatment machine.
In some embodiments of the present application, the flexible substrate includes, but is not limited to, polyurethane, polydimethylsiloxane (PDMS), rubber, copolyester (Ecoflex), polyethylene terephthalate (PET), polyvinyl chloride (PVC), paper base, and the like.
In some embodiments of the present application, the liquid flexible substrate material needs to adopt spin coating, slit coating, electrospray process, electric field driven spray deposition micro-nano 3D printing technology; the solid thermoplastic flexible substrate material can be prepared by adopting an electric field driven melting jet micro-nano 3D printing technology, a flexible substrate is manufactured on a base plate, and the flexible substrate is heated and solidified.
In some embodiments of the present application, the substrate includes, but is not limited to, glass, plastic, and silicon wafers.
In some embodiments of the present application, the flexible substrate has a thickness of 500nm-5mm and an area of 0.1cm 2 -1cm 2 。
In some embodiments of the present application, in step (2), the master mold making method comprises: according to the designed interdigital structure, an electric field driven jet deposition micro-nano 3D printing technology is adopted, the interdigital structure with a large height-width ratio and high resolution is printed on the flexible substrate by the conductive material, and low-temperature sintering and curing are carried out to form a female die (conductive substrate).
In some embodiments of the present application, the conductive material includes, but is not limited to, a flexible conductive silver paste, a conductive ink, a mixture of TPU and silver, a nano silver conductive ink, a nano copper conductive ink, a silver nanowire, a graphene conductive ink, or/and a carbon nanotube conductive ink.
In some embodiments of the present application, the conductive master interdigital structure has a line width of 500nm to 1mm.
In some embodiments of the present application, the aspect ratio is up to 6: 1.
In some embodiments of the present application, the interdigitated structure includes a straight line and a curved line, preferably a curved line, which can improve its tensile properties.
In some embodiments of the present application, the low-temperature sintering curing is to volatilize an internal solvent to achieve a better conductive effect, the sintering temperature is between 80 ℃ and 150 ℃, the sintering time is between 30min and 120min, and different sintering conditions are selected according to different conductive materials.
In some embodiments of the present application, in the step (3), the electrode material is prepared into a polymerization solution, and a layer of the electrode material is deposited on the master model by setting parameters through an electrochemical polymerization process by using a three-electrode system.
In some embodiments of the present application, the electrode material includes, but is not limited to, polypyrrole (PPy), polyaniline (PANI), polythiophene (PTh), and derivatives thereof, such as high molecular conductive polymers like poly-3, 4-ethylenedioxythiophene (PEDOT), poly-3-4-fluorophenylthiophene (PFPT), and poly-3-methylthiophene (PMeT).
In some embodiments of the present application, the electrochemical polymerization process includes potentiostatic, galvanostatic, and cyclic voltammetry, and the growth rate and thickness of the electrode material are controlled by adjusting the deposition time, current density, and deposition potential.
In some embodiments of the present application, in the three-electrode system, the saturated calomel electrode is a reference electrode, the platinum sheet is a counter electrode, and the master mold is a working electrode.
In some embodiments of the present application, in step (4): preparing a suitable solid electrolyte according to the electrode material, coating the suitable solid electrolyte in the electrode material and the insulating gap, and standing for curing.
In some embodiments of the present application, the solid electrolyte includes, but is not limited to, H 3 PO 4 /PVA、H 2 SO 4 PVA, KCl/PVA, liCl/PVA and LiClO 4 PVA and other gel electrolytes.
In some embodiments of the present application, the insulation gap is a distance between adjacent electrodes, and by reducing the insulation gap, the time for ions to pass through can be reduced, and the electrochemical performance can be improved, and the width of the insulation gap is 0.001mm-1mm.
In some embodiments of the present application, in step (5): and (3) selecting the same material as the flexible substrate, uniformly coating a layer above the electrolyte and the flexible substrate by adopting the same process as the step (1), and sealing the electrolyte and the flexible substrate to finish the manufacturing of the miniature flexible super capacitor.
In some embodiments of the application, the flexible miniature super capacitor prepared by the manufacturing method is provided, and the surface capacitance of the flexible miniature super capacitor can reach 27-1200mF/cm at the scanning speed of 10mV/s 2 The energy density is 0.00000375 KW.h/cm 2 -0.000167KW.h/cm 2 The power density is 0.000135KW/cm 2 -0.006012KW/cm 2 。
Compared with the prior art, the beneficial effect of this application is:
the method combines the advantages of micro-nano 3D printing female die and electrochemical polymerization, and realizes efficient and low-cost batch manufacturing of the flexible micro supercapacitor with high aspect ratio and high resolution.
The following significant advantages are achieved:
(1) The manufacturing method solves the problem that the existing technologies such as etching and the like cannot realize the manufacturing of the interdigital structure with high resolution and large aspect ratio, and realizes the efficient and low-cost batch manufacturing of the miniature flexible super capacitor.
(2) The patterning of the conductive high molecular polymer is successfully realized, the surface area is increased, the capacitance is increased, and the electrochemical performance of the supercapacitor is greatly improved.
(3) By adopting an electrochemical polymerization process, the thickness and the insulation gap of the electrode material can be controlled, so that the electrochemical performance of the supercapacitor is improved.
(4) The manufactured micro super capacitor has good mechanical property and electrochemical property, and can be widely applied to a plurality of fields of portable wireless communication systems, micro electro mechanical systems, biological wireless sensors, multifunctional micro/nano systems, micro robots, wearable/implantable medical equipment and the like.
(5) The process is simple, the manufacturing cost is low, expensive facilities are not needed, the process adaptability is strong, and the controllability is good.
(6) The usable material is wide, the utilization rate is high, an ultra-static environment is not needed, and the environment is not polluted.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic process flow diagram of the present application for making a flexible micro supercapacitor;
FIG. 2 is a schematic view of a linear interdigital electrode in accordance with example 1 of the present application;
fig. 3 is a schematic view of a curved interdigital electrode in accordance with example 2 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
Various fabrication techniques such as photolithography, plasma etching, laser scribing and ink jet printing methods face many deficiencies and limitations in achieving flexible micro-supercapacitors based on conductive high molecular polymers, such as processing cost, fabrication cycle time, interdigitated structure, resolution, aspect ratio, etc. The manufacturing method of the conductive polymer flexible micro supercapacitor based on the micro-nano 3D printing female die and electropolymerization successfully solves the problems.
Manufacturing a micro flexible substrate on a substrate; an electric field driven jet deposition micro-nano 3D printing technology is adopted, and an interdigital structure with a large aspect ratio and high resolution is printed on a micro flexible substrate by a conductive material to serve as a female die (a conductive substrate); depositing an electrode material on the master mold by using an electrochemical polymerization process; preparing a solid electrolyte, and coating the solid electrolyte on the electrode material and the insulating gap; and sealing the substrate by adopting a flexible substrate material to obtain the miniature flexible super capacitor with high resolution and large aspect ratio.
Example 1
The micro flexible supercapacitor is manufactured by adopting an electric field driven jet deposition micro-nano 3D printing technology and an electrochemical polymerization process, PDMS is selected as a micro flexible substrate, conductive silver paste 201s (flexible conductive silver paste) is selected as a conductive substrate, PPy is selected as an electrode material, a solid electrolyte is LiCl/PVA gel electrolyte, and a linear interdigital structure is selected as shown in figure 2. The process flow is shown in figure 1, and the specific preparation steps comprise:
(1) Fabrication of micro flexible substrate
Adopting common glass as a substrate; firstly, cleaning a glass substrate, carrying out ultrasonic treatment on the glass substrate for 10min by using deionized water, and then drying the glass substrate by using nitrogen. Preparing a PDMS film on a glass substrate by adopting an electric field driven jet deposition micro-nano 3D printing technology, and selecting an appropriate amount of Dow Corning 184 canning glue with the thickness of about 1 mu m and the area of 0.3cm 2 Heating and curing PDMS in a vacuum environment, wherein the heating temperature is set to 85 ℃, and the heating time is set to 20min.
(2) Making a master die
Designing a linear interdigital structure program, guiding the linear interdigital structure program into printing equipment, selecting a glass sprayer with the caliber of 30 micrometers, setting air pressure to be 200KPa, setting the distance between the sprayer and a substrate to be 50 micrometers, setting voltage to be 850V, lifting each layer of sprayer to be 15 micrometers, setting the printing speed to be 2mm/s, adopting an electric field driving jet deposition micro-nano 3D printing technology, printing the stretchable silver paste on PDMS to form an interdigital structure with high aspect ratio and high resolution, using the interdigital structure as a conductive substrate (female die), placing the interdigital structure in a drying box, setting the temperature to be 150 ℃, sintering for 30min, and taking out the interdigital structure. The line width of the master model is 10 μm, the insulation gap is 50 μm, and the aspect ratio is 6: 1.
(3) Depositing electrode material
Preparing a polymerization solution: dissolving 1mmol of pyrrole, 1mmol of p-toluenesulfonic acid and 1mmol of dodecylbenzene sulfonic acid in 30ml of distilled water, and carrying out ultrasonic treatment for 5min to obtain a polymer electrolyte;
selecting an electrochemical workstation, adopting a constant potential polymerization method, utilizing a three-electrode system, taking a saturated calomel electrode as a reference electrode, a platinum sheet as a counter electrode and a female die as a working electrode, immersing the three electrodes into a solution, setting the polymerization potential to be 0.6V and the polymerization time to be 2400s, depositing a polypyrrole film on the female die, tightly attaching the polypyrrole film to a conductive substrate, wherein the thickness of the polypyrrole film is about 10 mu m, and drying a sample in vacuum at 60 ℃ after polymerization is completed to obtain the Ag/PPy flexible electrode.
(4) Formulating solid electrolytes
The solid electrolyte is LiCl/PVA gel electrolyte, and 1.0g of PVA powder is added into 1.0mol of Li - Heating to 85 ℃ under vigorous stirring in the LiCl aqueous solution until the solution becomes clear and transparent, and cooling to room temperature for later use; and uniformly coating the prepared gel electrolyte on the PPy film and the insulation gap, and standing for 12 hours to solidify the gel electrolyte.
(5) Package structure
And printing a layer of PDMS on the electrolyte and the micro flexible substrate by adopting a 3D printing technology to completely wrap the PDMS, heating and curing the PDMS in a vacuum environment, wherein the heating temperature is set to 85 ℃, the heating time is set to 20min, and curing is carried out to obtain the micro flexible supercapacitor.
Example 2
The micro flexible supercapacitor is manufactured by adopting an electric field driven jet deposition micro-nano 3D printing technology and an electrochemical polymerization process, ecoflex is selected as a micro flexible substrate, a TPU and Ag mixture is selected as a conductive material, PANI is selected as an electrode material, and a solid electrolyte is H 2 SO 4 The PVA gel electrolyte adopts a curve interdigital structure. The preparation method comprises the following specific steps:
(1) Fabrication of micro flexible substrate
Adopting a silicon wafer as a substrate: firstly, cleaning a silicon wafer substrate, carrying out ultrasonic treatment on the silicon wafer substrate for 10min by using deionized water, then drying the silicon wafer substrate by using nitrogen, preparing a layer of Ecoflex film on a glass substrate by adopting an electric field driven spray deposition micro-nano 3D printing technology, selecting Smooth-on and Ecoflex 00-30 platinum cured silica gel, wherein the mass preparation ratio of A to B is 1: 1, the thickness of the Ecoflex film is about 10 mu m, and the area of the Ecoflex film is 0.2cm 2 Ecoflex is heated and cured in a vacuum environment, the heating temperature is set to 85 ℃, and the heating time is set to 60min.
(2) Making a female die
Preparing a conductive material: dissolving 3g of TPU in 5ml of the solution of the silver halide, adding 10g of silver flakes, adding 3g of carbon nano tubes in 3 times, and ultrasonically stirring for 30 minutes to obtain a mixture solution of the TPU and the Ag.
Designing a curve interdigital structure program, guiding the curve interdigital structure program into printing equipment, selecting a stainless steel spray head with the model number of 30, setting the caliber to be 120 microns, setting the air pressure to be 250KPa, setting the distance between the spray head and a substrate to be 200 microns, setting the voltage to be 880V, lifting each layer of spray head to be 100 microns, setting the printing speed to be 2mm/s, adopting an electric field driving jet deposition micro-nano 3D printing technology, printing an interdigital structure with high aspect ratio and high resolution on an Ecoflex mixture to be used as a conductive substrate (female die), placing the conductive substrate in a drying box, setting the temperature to be 80 ℃, sintering for 120min, and taking out. The line width of the female die is 100 mu m, the insulation gap is 100 mu m, and the aspect ratio is 5:1, the curve has an arc of curvature of about 30 °.
(3) Depositing electrode material
Preparing a polymerization solution: and 0.1M aniline monomer was dissolved in 0.5M H 2 SO 4 And (4) performing ultrasonic treatment on the solution for 5min to prepare the polymer electrolyte.
The master model was incubated at 40 ℃ in HCl solution (30 ml H) 2 O +70ml HCl) for 20 minutes, and hydrophilizing the master model. Then, the master model is washed to be neutral by secondary water and dried for standby.
Selecting an electrochemical workstation, adopting cyclic voltammetry, utilizing a three-electrode system, taking a saturated calomel electrode as a reference electrode, a platinum sheet as a counter electrode and a female die as a working electrode, immersing the three electrodes into a solution, setting the polymerization rate to be 50mV/s and the polymerization time to be 400s, depositing polyaniline on the female die, tightly attaching a polyaniline film to a conductive substrate, wherein the thickness of the polyaniline film is about 5 mu m, and drying a sample at 60 ℃ in vacuum after polymerization is completed to obtain the Ag/PANI flexible electrode.
(4) Formulating solid electrolytes
H is selected as solid electrolyte 2 SO 4 PVA gel electrolyte, 5g of H 2 SO 4 PVA/H was prepared by adding 5g of PVA and 50mL to a flask and stirring continuously at 90 ℃ for 2 hours until a clear transparent solution formed 2 SO 4 And cooling the solid electrolyte to room temperature for later use. The prepared gel electrolyte is evenly coated on the PANI film and the insulation gap,standing for 12h to solidify.
(5) Package structure
Printing a layer of Ecoflex on an electrolyte and a micro flexible substrate by adopting a 3D printing technology to completely wrap the Ecoflex, heating and curing the Ecoflex in a vacuum environment, wherein the heating temperature is set to 80 ℃, the heating time is set to 120min, and curing to obtain the flexible micro supercapacitor.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not necessarily depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.
Claims (19)
1. A manufacturing method of a flexible micro super capacitor is characterized by comprising the following steps: (1) manufacturing a flexible substrate on a substrate; (2) Printing an interdigital structure female die by adopting an electric field driven jet deposition micro-nano 3D printing technology, namely printing an interdigital structure with a large height-width ratio and high resolution on a flexible substrate by adopting the electric field driven jet deposition micro-nano 3D printing technology according to the designed interdigital structure, and sintering and curing to form the female die; (3) Depositing an electrode material on the master die through an electrochemical polymerization process; (4) uniformly coating the solid electrolyte on the electrode material; (5) And sealing and manufacturing the flexible micro super capacitor.
2. The method of claim 1, wherein the flexible substrate comprises Polydimethylsiloxane (PDMS), rubber, copolyester (Ecoflex), polyethylene terephthalate (PET), polyvinyl chloride (PVC), paper base.
3. The method according to claim 1, wherein in the step (2), the line width of the master mold of the interdigital structure is 500nm to 1mm, and the aspect ratio is up to 6: 1.
4. The method of claim 1, wherein the conductive material comprises a flexible conductive silver paste, a conductive ink, a TPU and silver mixture, a nano silver conductive ink, a nano copper conductive ink, a silver nanowire, a graphene conductive ink, or/and a carbon nanotube conductive ink.
5. The method as claimed in claim 1, wherein the sintering and curing process is a low temperature sintering and curing process, which volatilizes the internal solvent to achieve better electrical conductivity, the sintering temperature is between 80 ℃ and 150 ℃, the sintering time is between 30min and 120min, and different sintering conditions are selected according to different conductive materials.
6. The method according to claim 1, wherein in the step (3), the electrode material is prepared into a polymerization solution, and a layer of the electrode material is deposited on the master model by setting parameters through an electrochemical polymerization process by using a three-electrode system.
7. The method of claim 1, wherein the electrode material includes but is not limited to polypyrrole, polyaniline, polythiophene and their derivatives.
8. The method for manufacturing a flexible micro supercapacitor according to claim 1, wherein in the step (4): preparing a suitable solid electrolyte according to the electrode material, coating the suitable solid electrolyte in the electrode material and the insulating gap, and standing for curing.
9. The method for manufacturing a flexible micro supercapacitor according to claim 1, wherein in the step (5): and (3) selecting the same material as the flexible substrate, uniformly coating a layer above the electrolyte and the flexible substrate by adopting the same process as the step (1), and sealing the electrolyte and the flexible substrate to finish the manufacturing of the miniature flexible super capacitor.
10. The manufacturing method of the flexible micro supercapacitor according to claim 1, wherein a liquid flexible substrate material needs to adopt spin coating, a slit coating method, an electrospray process, an electric field driven jet deposition micro-nano 3D printing technology; the solid thermoplastic flexible substrate material can be prepared by adopting an electric field driven melting jet micro-nano 3D printing technology, a flexible substrate is manufactured on a base plate, and the flexible substrate is heated and solidified.
11. The method as claimed in claim 1, wherein the flexible substrate has a thickness of 500nm-5mm and an area of 0.1cm 2 -1cm 2 。
12. The method of claim 3, wherein the interdigitated structure comprises straight and curved lines.
13. The method of claim 12 wherein said interdigitated structure is curved to enhance its tensile properties.
14. The method as claimed in claim 6, wherein the electrochemical polymerization process comprises potentiostatic method, galvanostatic method and cyclic voltammetry, and the growth rate and thickness of the electrode material are controlled by adjusting deposition time, current density and deposition potential.
15. The method according to claim 14, wherein in the three-electrode system, the saturated calomel electrode is a reference electrode, the platinum sheet is a counter electrode, and the master model is a working electrode.
16. The method as claimed in claim 7, wherein the electrode material is poly (3, 4-ethylenedioxythiophene), poly (3-4-fluorophenylthiophene) or poly (3-methylthiophene) polymer.
17. The method of claim 8 wherein the solid electrolyte includes but is not limited to H 3 PO 4 /PVA、H 2 SO 4 PVA, KCl/PVA, liCl/PVA and LiClO 4 PVA gel electrolyte.
18. The method as claimed in claim 8, wherein the insulation gap is a distance between adjacent electrodes, and the insulation gap is reduced to reduce ion passage time and improve electrochemical performance, and has a width of 0.001mm to 1mm.
19. The flexible micro-supercapacitor prepared by the method for manufacturing the flexible micro-supercapacitor according to any one of claims 1 to 17, wherein the surface capacitance of the flexible micro-supercapacitor can reach 27-1200mF/cm at a scanning rate of 10mV/s 2 The energy density is 0.00000375 KW.h/cm 2 -0.000167KW·h/cm 2 The power density is 0.000135KW/cm 2 -0.006012KW/cm 2 。
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