CN113223861A - Planar ultrathin flexible high-voltage supercapacitor and preparation method thereof - Google Patents
Planar ultrathin flexible high-voltage supercapacitor and preparation method thereof Download PDFInfo
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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
- H01G11/22—Electrodes
-
- 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
- H01G11/10—Multiple hybrid or EDL capacitors, e.g. arrays or modules
-
- 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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
-
- 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
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- 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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- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
本发明公开了一种平面式超薄柔性高电压超级电容器及其制备方法。具体以超薄柔性金属片作导电串联介质，相邻金属片边沿喷涂聚四氟乙烯或者涂覆耐高温环氧树脂AB胶作绝缘层，采用热固化聚酰亚胺前驱液或者粘贴PI薄膜的方法在金属片上获得聚合物层，通过激光加工PI固化层/薄膜制备石墨烯电极材料，在其表面滴涂水凝胶电解质并粘贴铜箔作集流体完成超级电容器的封装。得益于中间薄层金属片的串联效果，最终可输出10V以上的高电压；由于金属片和PI固化层/薄膜厚度可控，可实现超薄串联结构设计；且金属片优异的柔韧性和强度高度适用于制备柔性高电压超级电容器。其可作为能量存储/补给装置，在可穿戴器件和集成电子领域颇具应用前景。
The invention discloses a planar ultra-thin flexible high-voltage supercapacitor and a preparation method thereof. Specifically, an ultra-thin flexible metal sheet is used as the conductive series medium, and the edge of the adjacent metal sheet is sprayed with polytetrafluoroethylene or coated with high temperature epoxy resin AB glue as an insulating layer, and a thermally cured polyimide precursor liquid or a PI film is used. Methods The polymer layer was obtained on the metal sheet, the graphene electrode material was prepared by laser processing the PI cured layer/film, the hydrogel electrolyte was dripped on the surface and the copper foil was pasted as the current collector to complete the packaging of the supercapacitor. Thanks to the series connection effect of the middle thin metal sheet, a high voltage of more than 10V can be output finally; due to the controllable thickness of the metal sheet and PI cured layer/film, ultra-thin series structure design can be realized; and the excellent flexibility and The strength is highly suitable for making flexible high-voltage supercapacitors. It can be used as an energy storage/replenishment device and has great application prospects in the fields of wearable devices and integrated electronics.
Description
Technical Field
The invention belongs to the technical field of super capacitors, and particularly relates to a planar ultrathin flexible high-voltage super capacitor and a preparation method thereof.
Background
Due to the advantages of being light, thin, portable, flexible, long in cycle life, high in power/energy density and the like, the planar flexible high-voltage super capacitor is frequently applied to occasions such as wearable facilities and integrated microcircuit systems as a power/energy supply device, and can provide voltage output and energy supply in a certain range according to needs. In practical application, the application voltage of a high-density integrated electronic chip/circuit board is mostly concentrated to be 3-5V, the application voltage of small electronic devices (such as a smart watch, an electronic clock, a temperature/humidity meter and the like) and wearable flexible electronic skin/sensors is basically within 3V, and the rated voltage of a mobile charging power supply is 5V. However, the stable operating voltage of the super capacitor without the series structure is generally about 1V, which is mainly limited by the hydrolysis voltage of the electrolyte. The existing manufacturing method completes the packaging of a series high-voltage structure by directly processing an electric connection part on a flexible substrate, is beneficial to constructing a high-voltage flexible super capacitor, but does not well utilize the substrate/the upper surface and the lower surface of the substrate to carry out series design, so that the whole structure of the super capacitor is difficult to further optimize, and the more compact high-voltage packaging is realized. Therefore, in the application of a high-density device integration system, the high-voltage super capacitor still has the problems of structural redundancy, compactness, low integration performance and the like. Although compact high voltage structures can be made using high precision manufacturing methods such as femtosecond laser processing, electrical inkjet printing, and the like, higher manufacturing costs are undoubtedly incurred.
Disclosure of Invention
The invention aims to provide a planar ultrathin flexible high-voltage super capacitor and a preparation method thereof, aiming at solving the problems that the output voltage of the super capacitor is not high enough, the structure is compact and low, the series electric connection part is redundant, the series high-voltage preparation process is complicated and the like, so as to meet the requirements of wearable flexible devices and high-density integrated electronic equipment on high voltage. Specifically, a metal sheet is used as a high-elasticity matrix and a series connection electric connection medium, a polyimide curing layer with a certain thickness is attached to the upper surface layer and the lower surface layer of the metal sheet through a thermosetting process, an interdigital patterned electrode (laser-induced graphene) and an electric connection part (aiming at realizing the series connection of a plurality of super capacitors) are prepared under different powers by adopting a laser processing method, the super capacitors are packaged by utilizing a conductive current collector, a hydrogel electrolyte is coated on the surfaces of the graphene electrodes, the overall thickness of the prepared super capacitor can be controlled below 0.5mm, the high-voltage output of more than 10V can be realized, and meanwhile, the super capacitor has excellent flexibility attached to the metal sheet. The ultra-thin High Voltage Super Capacitor (HVSCs) has a wide application prospect in the fields of wearable flexible devices and integrated electronics.
The technical scheme of the invention is as follows.
A plane type ultrathin flexible high-voltage super capacitor comprises a polymer thin layer, an electric conduction part, an insulating coating, a graphene electrode and a conductive metal sheet; the polymer thin layer includes a first polymer thin layer and a second polymer thin layer, and the electric conduction portion includes a first electric conduction portion and a second electric conduction portion; the graphene electrodes include a first graphene electrode and a second graphene electrode;
the conductive metal sheets are separated from each other by the insulating coating to form a plurality of sections; the upper surface and the lower surface of the conductive metal sheet are respectively provided with a first polymer thin layer and a second polymer thin layer; a first conductive part is arranged on the first polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent first conductive parts are insulated; a second conductive part is arranged on the second polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent second conductive parts are insulated; a first graphene electrode and a second graphene electrode are respectively arranged on the first polymer thin layer and the second polymer thin layer;
the current is circulated to second graphite alkene electrode through first electric conduction part, electrically conductive sheetmetal, second electric conduction part by the first graphite alkene electrode of same section, and second electric conduction part, electrically conductive sheetmetal, the first electric conduction part circulation of passing through the back section by the second graphite alkene electrode of preceding section simultaneously to the first graphite alkene electrode of same section.
Further, the conductive metal sheet is a high-flexibility conductive metal sheet.
Further, the conductive metal sheet is one of spring steel, beryllium bronze and phosphor bronze; the electric conduction part is conductive silver paste or sprayed gold; the graphene electrode is interdigital.
Further, the interdigital shape is a rectangle, the number of the rectangles is one of eight, ten and twelve, and the single size is 1.5 multiplied by 10 mm.
Further, the insulating part is polytetrafluoroethylene spray or high-temperature-resistant epoxy resin AB glue; the polymer thin layer is a solidified layer formed by thermally curing a polymer adhesive tape or a precursor liquid.
Furthermore, the adhesive tape is one of a polymer polyimide adhesive tape and a polyetherimide adhesive tape containing aromatic rings and imide structural units, and is attached by a sticking mode; the curing layer is attached by taking polyimide as a precursor solution in a thermal curing mode after brushing, wherein the thermal curing process is heating and heat preservation with multiple temperature gradients under low vacuum degree; the precursor liquid is one of thermoplastic liquid or hot solid-liquid.
Further, the conductive metal sheet has one or more of the dimensions of 25/30 × 30mm, 25/30 × 5mm and 25/30 × 15mm, and has one of the thicknesses of 0.02mm, 0.03mm and 0.04 mm; the high-temperature-resistant epoxy resin AB glue is one of TH-801, TH-802, TE-9249 and TE-9128, and has excellent thermal stability in the high-temperature thermocuring process; the thickness of the polyimide adhesive tape is one of 0.04mm, 0.05mm, 0.055mm and 0.08 mm.
Further, a first graphene electrode on the first section of conductive metal sheet and a second graphene electrode on the last section of conductive metal sheet are provided with conductive current collectors; the conductive current collector is one or more than two of nickel foil, copper foil, silver paste, silver nanowires and gold nanoparticles; gel electrolyte is arranged on all the first graphene electrodes and the second graphene electrodes.
The preparation method of the planar ultrathin flexible high-voltage supercapacitor comprises the following steps:
(1) cutting conductive metal sheets with different sizes, carrying out electric insulation treatment on the side edge parts of the conductive metal sheets to form electric insulation parts, and attaching polymer thin layers on the upper and lower surfaces of the conductive metal sheets;
(2) preparing a patterned graphene electrode (LIG) by processing a polymer layer by using laser, adjusting the laser power to completely remove the polymer layer of the conductive part, and coating conductive silver paste or spraying gold for electric connection treatment to realize the electric conduction of the graphene electrode and a conductive metal sheet;
(3) the super capacitor is packaged by utilizing the conductive current collector, the gel electrolyte is dripped to the graphene electrode part, and the output of different high voltages can be realized by controlling the series connection quantity of the super capacitor.
Further, in the step (1), the electrical insulation treatment is one of spraying Polytetrafluoroethylene (PTFE) spray or dropping high-temperature-resistant epoxy resin AB glue; the polymer layer is one of a polymer Polyimide (PI) film and a polyetherimide film containing aromatic rings and imide structural units.
Further, in the step (2), the laser is carbon dioxide infrared laser; the scanning speed of the carbon dioxide infrared laser is 100mm/s, the power for processing the graphene electrode part is 9.6%, and the power for processing the electric conduction part is 12%; the electric connection treatment is one of gold spraying or silver paste coating.
Further, in the step (3), the conductive current collector is added in one of pasting, brushing, spraying and electrochemical deposition; the gel electrolyte is a mixture of a polymer skeleton and a plasticizer, and the addition mode is one of dripping, brushing and spin coating; the polymer skeleton is one of polyacrylate, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile, polyvinylidene fluoride-co-hexafluoropropylene, polymethyl methacrylate and poly (ethylene glycol) blended poly (acrylonitrile); the plasticizer is a mixture of an organic solvent and a supporting electrolyte; the organic solvent is two or more of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, butyrolactone and tetrahydrofuran; the supporting electrolyte is one of potassium chloride, potassium perchlorate, sulfuric acid, phosphoric acid, potassium hydroxide and potassium chloride; the spin coating parameter is 500-600r/min, the time is 3-5min, and the thickness of the cured layer is 0.2-0.5 mm.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the phosphor copper strip as the elastic electric connection matrix, can be attached to the super capacitor with excellent flexibility and has excellent CV performance in a bending or torsion state.
2. The invention firstly proposes that the serial packaging is designed on the upper surface and the lower surface of the elastic metal sheet substrate, thereby realizing a more compact structure.
3. The invention can prepare the ultra-thin super capacitor with the whole thickness (including the thickness of the electrolyte layer) below 0.5mm by controlling the thicknesses of the phosphor copper strip and the polyimide film/cured layer; the high-voltage output of more than 10V can be realized in a small size range by adjusting the series number of the super capacitors.
4. The high-voltage super capacitor prepared on the basis of the elastic metal sheet substrate is suitable for high-density high-voltage facilities such as wearable electronic devices, integrated microcircuits and the like, and has universality.
Drawings
Fig. 1 is a front, back and cross-sectional layout of the planar ultra-thin flexible high voltage supercapacitor of the present invention, wherein the straight line with arrows represents the series conducting circuit.
Fig. 2 is a design diagram of the dimension of the interdigital graphene electrode of the planar ultrathin flexible high-voltage supercapacitor according to the present invention.
Fig. 3 is a tensile stress strain plot of the resulting supercapacitor of example 1 with a phosphorus-free copper sheet (PCS).
Fig. 4 is a graph of CV performance of the planar ultra-thin flexible high voltage supercapacitor of example 1 under different bending conditions.
Fig. 5 is a graph of CV performance of the planar ultra-thin flexible high voltage supercapacitor of example 1 for different numbers of repeated twists.
Fig. 6 is a thickness diagram of the whole of the planar ultrathin flexible high-voltage supercapacitor package of example 1 after the package is completed.
Fig. 7 is a graph of CV performance of the planar ultra-thin flexible high voltage supercapacitor of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are carried out in the light of the technical solutions of the present invention to facilitate a full understanding of the present invention. It should be understood that the present invention is not limited to the following embodiments, and modifications and equivalents may be made without departing from the spirit and scope of the present invention as defined in the appended claims.
The invention relates to a plane type ultrathin flexible high-voltage supercapacitor, which comprises a polymer thin layer 1, an electric conduction part 2, an insulating coating 3, a graphene electrode 5 and a conductive metal sheet 6; the polymer thin layer 1 includes a first polymer thin layer and a second polymer thin layer, and the electric conduction section 2 includes a first electric conduction section and a second electric conduction section; the graphene electrode 5 comprises a first graphene electrode and a second graphene electrode;
the conductive metal sheets 6 are separated from each other by the insulating coating 3 to form a plurality of sections; the upper surface and the lower surface of the conductive metal sheet 6 are respectively provided with a first polymer thin layer and a second polymer thin layer; a first conductive part is arranged on the first polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent first conductive parts are insulated; a second conductive part is arranged on the second polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent second conductive parts are insulated; a first graphene electrode and a second graphene electrode are respectively arranged on the first polymer thin layer and the second polymer thin layer;
a conductive current collector 4 is arranged on the first graphene electrode on the first section of conductive metal sheet and the second graphene electrode on the last section of conductive metal sheet; gel electrolyte 7 is arranged on all the first graphene electrode and the second graphene electrode.
The current is circulated to second graphite alkene electrode through first electric conduction part, electrically conductive sheetmetal, second electric conduction part by the first graphite alkene electrode of same section, and second electric conduction part, electrically conductive sheetmetal, the first electric conduction part circulation of passing through the back section by the second graphite alkene electrode of preceding section simultaneously to the first graphite alkene electrode of same section.
Example 1
(1) The phosphor copper strip C5191 with the thickness of 20 mu m is cut into three dimensions of 25 multiplied by 30mm (2 sheets), 25 multiplied by 5mm (4 sheets) and 25 multiplied by 15mm (3 sheets), a preservative film is used for wrapping the upper surface and the lower surface of the phosphor copper strip, polytetrafluoroethylene spray OKS 571 is sprayed on the side edge of the phosphor copper strip, then 9 phosphor copper strips are sequentially placed on an experimental platform according to the graph 1, and the relative positions of the phosphor copper strips are fixed by using double-sided adhesive.
(2) And respectively sticking the polyimide tapes Kapton with the thickness of 40 mu m on the upper and lower surfaces of the phosphor copper sheet, and in the sticking process, using a roller to assist in imprinting at a constant speed (130-.
(3) The scanning speed of carbon dioxide infrared laser is set to be 100mm/s, the power is 9.6%, the laser focal length is 8mm, and interdigital graphene electrodes (8 pairs) shown in figure 2 are processed on the upper surface and the lower surface of a phosphor copper sheet in sequence by utilizing a laser-induced polyimide adhesive tape; keeping the laser scanning speed and the relative position unchanged, increasing the output power to 12%, completely carbonizing and removing the polyimide adhesive tape of the electric conduction part, manually coating a proper amount of conductive silver paste on the electric conduction part by using an injector, standing for 10-15 minutes to solidify the silver paste, and ensuring that the interdigital graphene electrode is electrically connected with the phosphor copper sheet.
(4) Weighing 3g of polyvinyl alcohol powder (with the molecular weight of 85000-98000) by using an electronic balance, adding the polyvinyl alcohol powder into 30mL of deionized water, magnetically stirring (600r/min) in a water bath at 90 ℃ for 45 minutes until the solution becomes clear, naturally cooling and standing the gel solution at room temperature for 60 minutes, injecting 3.5mL of phosphoric acid (with the mass fraction of 85% as an analytical grade) into the gel solution, and magnetically stirring (600r/min) at room temperature for 35 minutes to obtain PVA/H3PO4A gel electrolyte.
(5) A proper amount of conductive silver paste is manually coated on the current collector connecting parts on the upper side and the lower side of the interdigital graphene electrode by using an injector, then a copper foil (5mm in width) is pasted to serve as a connecting part with external detection equipment, and the copper foil is fixed by using a polyimide adhesive tape, so that the conductive current collector is ensured to be in close contact with a graphene electrode material.
(6) 3mL of gel electrolyte is dripped on each group of interdigital graphene electrode parts on the upper surface of the phosphor copper sheet, a syringe needle is used for assisting the uniform distribution of the electrolyte, the phosphor copper sheet is placed for 24 hours at room temperature until the electrolyte is completely solidified after the moisture is volatilized, then the steps are repeated on the lower surface of the phosphor copper sheet, and finally the packaging of the 10V high-voltage super capacitor is completed.
If the phosphorus-free copper sheet intermediate layer is used as a flexible substrate and a series medium, the polyimide films on the upper layer and the lower layer cannot realize three-dimensional packaging because the series electric connection part of the upper layer and the lower layer cannot be constructed.
Fig. 3 shows that the addition of the phosphor copper sheet can significantly improve the tensile strength of the high voltage flexible supercapacitor to 18.23Mpa, while the strain is only 6.83%.
The excellent flexibility of the high voltage supercapacitor is shown by the fact that stable CV performance can be maintained under different degrees of bending conditions (see FIG. 4) or different times of repeated torsion (see FIG. 5), wherein the capacity retention is 97.78% when the high voltage supercapacitor is bent by 180 degrees, and the capacity retention is 98.31% after the high voltage supercapacitor is repeatedly twisted for 100 times, and the high voltage supercapacitor and the supercapacitor are basically not obviously attenuated compared with the initial state.
Fig. 6 shows the overall thickness of the high voltage supercapacitor after packaging is completed to be 0.48 mm.
Fig. 7 shows that the output voltage of the high-voltage super capacitor after the packaging is finished can reach 10V.
Example 2
(1) 10g of high-temperature epoxy resin (TH-801) A glue and 2.5g of B glue are weighed in a beaker, are stirred magnetically (500r/min) for 5min at room temperature until being mixed uniformly, and are sealed by a preservative film and then are kept stand for later use.
(2) Cutting a phosphor copper sheet C5111 with the thickness of 30 mu m into three dimensions of 30 multiplied by 30mm (2 sheets), 30 multiplied by 5mm (4 sheets) 5 and 30 multiplied by 15mm (3 sheets), sequentially placing 9 phosphor copper sheets on an experimental platform according to the figure 1, fixing the relative positions of the phosphor copper sheets by using double-sided adhesive, dripping a small amount of the mixed AB adhesive by using an injector, placing the mixed AB adhesive at the adjacent side edge of the phosphor copper sheets (each part is controlled within 0.05 mL), standing for 12h, and completely curing to realize the connection of the 9 phosphor copper sheets.
(2) Measuring 0.4-0.8mL of polyimide thermoplastic liquid by using an injector, dripping the polyimide thermoplastic liquid on the upper surfaces of the 9 phosphorus copper sheets, repeatedly brushing for several times by using a brush with the width of 5mm, standing for 1-3min to form a precursor liquid layer with a smooth surface, transferring the precursor liquid layer to a vacuum drying box, vacuumizing to-0.6 Mpa, and setting the thermal curing process as follows: heating to 100 deg.C at room temperature for 80min, and keeping the temperature at 100 deg.C for 30 min; heating to 150 deg.C at 100 deg.C for 50min, and keeping the temperature at 150 deg.C for 40 min; heating to 205 deg.C at 150 deg.C for 50min, and keeping the temperature at 205 deg.C for 45 min; and finally, closing the heating device, naturally cooling the drying box to room temperature, and opening the air inlet to take out the sample. The thickness of the polyimide curing layer prepared in sequence is 10-20 μm. And then, placing the sample in a diluted hydrochloric acid solution to etch an oxide layer formed on the lower surface of the phosphor copper sheet in the thermosetting process, cleaning the oxide layer for several times by using alcohol and deionized water, wiping and drying, and repeating the steps to deposit a cured layer of 10-20 microns on the lower surface of the phosphor copper sheet.
(3) The scanning speed of carbon dioxide infrared laser is set to be 100mm/s, the power is 9.6%, the laser focal length is 8mm, and interdigital graphene electrodes (10 pairs) shown in figure 2 are processed on the upper surface and the lower surface of a phosphor copper sheet in sequence by utilizing a laser-induced polyimide adhesive tape; keeping the laser scanning speed and the relative position unchanged, increasing the output power to 15%, completely carbonizing, removing the polyimide curing layer of the electric conduction part, and then carrying out gold spraying treatment on the electric conduction part by using a mask to assist, so as to ensure that the interdigital graphene electrode is electrically connected with the phosphor copper sheet.
(4) Weighing 3g of polyvinyl alcohol powder (with the molecular weight of 85000-98000) by using an electronic balance, adding the polyvinyl alcohol powder into 30mL of deionized water, magnetically stirring (600r/min) in a water bath at 90 ℃ for 45 minutes until the solution becomes clear, naturally cooling and standing the gel solution at room temperature for 60 minutes, injecting 3.5mL of phosphoric acid (with the mass fraction of 85% as an analytical grade) into the gel solution, and magnetically stirring (600r/min) at room temperature for 35 minutes to obtain PVA/H3PO4A gel electrolyte.
(5) A proper amount of conductive silver paste is manually coated on the current collector connecting parts on the upper side and the lower side of the interdigital graphene electrode by using an injector, then a copper foil (5mm in width) is pasted to serve as a connecting part with external detection equipment, and the copper foil is fixed by using a polyimide adhesive tape, so that the conductive current collector is ensured to be in close contact with a graphene electrode material.
(6) 3mL of gel electrolyte is dripped on each group of interdigital graphene electrode parts on the upper surface of the phosphor copper sheet, a syringe needle is used for assisting the uniform distribution of the electrolyte, the phosphor copper sheet is placed for 24 hours at room temperature until the electrolyte is completely solidified after the moisture is volatilized, then the steps are repeated on the lower surface of the phosphor copper sheet, and finally the packaging of the 10V high-voltage super capacitor is completed.
The above disclosure is only illustrative of the present invention and should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A planar ultrathin flexible high-voltage supercapacitor is characterized by comprising a polymer thin layer (1), an electric conduction part (2), an insulating coating (3), a graphene electrode (5) and a conductive metal sheet (6); the polymer thin layer (1) includes a first polymer thin layer and a second polymer thin layer, and the electrically conducting section (2) includes a first electrically conducting section and a second electrically conducting section; the graphene electrode (5) comprises a first graphene electrode and a second graphene electrode;
the conductive metal sheets (6) are separated from each other by the insulating coating (3) to form a plurality of sections; the upper surface and the lower surface of the conductive metal sheet (6) are respectively provided with a first polymer thin layer and a second polymer thin layer; a first conductive part is arranged on the first polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent first conductive parts are insulated; a second conductive part is arranged on the second polymer thin layer and corresponds to each section of the conductive metal sheet, and the adjacent second conductive parts are insulated; a first graphene electrode and a second graphene electrode are respectively arranged on the first polymer thin layer and the second polymer thin layer;
the current is circulated to second graphite alkene electrode through first electric conduction part, electrically conductive sheetmetal, second electric conduction part by the first graphite alkene electrode of same section, and second electric conduction part, electrically conductive sheetmetal, the first electric conduction part circulation of passing through the back section by the second graphite alkene electrode of preceding section simultaneously to the first graphite alkene electrode of same section.
2. A planar ultra-thin flexible high voltage supercapacitor according to claim 1, characterized in that the conductive metal sheet (6) is one of spring steel, beryllium bronze and phosphor bronze; the electric conduction part (2) is conductive silver paste or sprayed gold; the graphene electrode (5) is interdigital.
3. The ultra-thin flexible high voltage planar supercapacitor of claim 2, wherein the fingers are rectangular, and the number of rectangles is one of eight, ten, and twelve.
4. The planar ultra-thin flexible high-voltage supercapacitor as claimed in claim 3, wherein the insulating coating (3) is polytetrafluoroethylene spray or high temperature resistant epoxy AB glue; the polymer thin layer (1) is a solidified layer formed by thermally curing a polymer adhesive tape or a precursor liquid.
5. The ultra-thin flexible high voltage supercapacitor of claim 4, wherein the conductive metal sheet has one or more of dimensions 25/30 x 30mm, 25/30 x 5mm, 25/30 x 15mm, and a thickness of one of 0.02mm, 0.03mm, and 0.04 mm; the high-temperature resistant epoxy resin AB glue is one of TH-801, TH-802, TE-9249 and TE-9128; the polymer thin layer (1) is a polyimide adhesive tape, and the thickness is one of 0.04mm, 0.05mm, 0.055mm and 0.08 mm.
6. The planar ultrathin flexible high-voltage supercapacitor according to any one of claims 1 to 5, characterized in that a first graphene electrode on the first section of conductive metal sheet and a second graphene electrode on the last section of conductive metal sheet are provided with conductive current collectors (4); the conductive current collector is one or more than two of nickel foil, copper foil, silver paste, silver nanowires and gold nanoparticles; gel electrolyte (7) is arranged on all the first graphene electrodes and the second graphene electrodes.
7. The method for preparing a planar ultra-thin flexible high voltage supercapacitor according to any one of claims 1 to 6, comprising the steps of:
(1) cutting conductive metal sheets with different sizes, carrying out electric insulation treatment on the side edge parts of the conductive metal sheets, and attaching polymer thin layers on the upper and lower surfaces of the conductive metal sheets;
(2) preparing a patterned graphene electrode by processing a polymer layer by using laser, adjusting the laser power to completely remove the polymer layer of the conductive part, and coating conductive silver paste or spraying gold to realize the electrical conduction of the graphene electrode and a conductive metal sheet;
(3) the super capacitor is packaged by utilizing the conductive current collector, the gel electrolyte is dripped to the graphene electrode part, and the output of different high voltages can be realized by controlling the series connection quantity of the super capacitor.
8. The planar ultra-thin flexible high-voltage supercapacitor as claimed in claim 7, wherein in step (1), the electrical insulation treatment is one of spraying polytetrafluoroethylene or dropping high temperature resistant epoxy AB glue; the polymer layer is one of a high-molecular polyimide film and a polyetherimide film containing aromatic rings and imide structural units.
9. The planar ultra-thin flexible high voltage supercapacitor according to claim 8, wherein in step (2), the laser is a carbon dioxide infrared laser; the scanning speed of the carbon dioxide infrared laser is 100mm/s, the power for processing the graphene electrode part is 9.6%, and the power for processing the electric conduction part is 12%; the electric connection treatment is one of gold spraying or silver paste coating.
10. The planar ultrathin flexible high-voltage supercapacitor according to claim 9, wherein in the step (3), the conductive current collector is added by one of pasting, brushing, spraying and electrochemical deposition; the gel electrolyte is a mixture of a polymer skeleton and a plasticizer, and the addition mode is one of dripping, brushing and spin coating; the polymer skeleton is one of polyacrylate, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile, polyvinylidene fluoride-co-hexafluoropropylene, polymethyl methacrylate and poly (ethylene glycol) blended poly (acrylonitrile); the plasticizer is a mixture of an organic solvent and a supporting electrolyte; the organic solvent is two or more of ethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, dimethylformamide, butyrolactone and tetrahydrofuran; the supporting electrolyte is one of potassium chloride, potassium perchlorate, sulfuric acid, phosphoric acid, potassium hydroxide and potassium chloride; the spin coating parameter is 500-600r/min, the time is 3-5min, and the thickness of the cured layer is 0.2-0.5 mm.
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