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CN109637846A - A kind of high voltage plane supercapacitor and preparation method thereof - Google Patents

A kind of high voltage plane supercapacitor and preparation method thereof Download PDF

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Publication number
CN109637846A
CN109637846A CN201811492487.4A CN201811492487A CN109637846A CN 109637846 A CN109637846 A CN 109637846A CN 201811492487 A CN201811492487 A CN 201811492487A CN 109637846 A CN109637846 A CN 109637846A
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supercapacitor
electrode
voltage
graphene
preparation
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CN201811492487.4A
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Inventor
吴忠帅
包信和
师晓宇
周锋
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CN201811492487.4A priority Critical patent/CN109637846A/en
Publication of CN109637846A publication Critical patent/CN109637846A/en
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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
    • H01G11/10—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
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
    • 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
    • H01G11/66—Current collectors
    • H01G11/72—Current collectors specially adapted for integration in multiple or stacked hybrid or EDL capacitors
    • 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)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

本发明公布了一种高电压平面型超级电容器及其制备方法，具体为以含有电极材料（石墨烯、碳纳米管、聚合物、氧化物、氢氧化物、硫化物和氮化物等）和添加剂的分散体系为油墨，采用印刷的方法，在任意绝缘基底上一步法制备出具有高电压的平面型超级电容器。所得的平面型超级电容器实现了电极、集流体和连接体的一体化制备以及多个平面超级电容器的串联集成，具有高的输出电压，能够与可打印的电子器件结合作为其功率源，具有广阔的市场前景。

The invention discloses a high-voltage planar supercapacitor and a preparation method thereof, specifically comprising electrode materials (graphene, carbon nanotubes, polymers, oxides, hydroxides, sulfides and nitrides, etc.) and additives The dispersion system is ink, and the method of printing is used to prepare a planar supercapacitor with high voltage on any insulating substrate in one step. The resulting planar supercapacitor realizes the integrated fabrication of electrodes, current collectors, and connectors, as well as the series integration of multiple planar supercapacitors, has high output voltage, and can be combined with printable electronic devices as its power source, with broad potential. market prospects.

Description

A kind of high voltage plane supercapacitor and preparation method thereof
Technical field
The invention belongs to energy storage fields, and in particular to a kind of high voltage plane supercapacitor and its preparation side Method.
Background technique
Supercapacitor is a kind of energy storage device of rising in recent years, relative to common lithium ion battery, its tool Have the advantages that power density is high, charge/discharge speed is fast, the service life is long.But it is generally limited to operating voltage (water in actual use 1.0V is generally below in system), it is difficult to reach the demand of electronic device normal work.It therefore, often will be multiple super by means of conducting wire Capacitor, which is together in series, improves operating voltage.But the introducing of conducting wire makes whole process become complicated, and can reduce super The specific capacity and energy density of grade capacitor.In addition, conducting wire connection in many places will be greatly reduced the integraty of entire device, it is unfavorable for Its further with the integrated application of electronic device.So being badly in need of developing new production method, while realizing the system of supercapacitor Standby and series connection.
Traditional supercapacitor is stacked gradually by collector, electrode, diaphragm, electrode, collector and is constituted, and interface is more, Step is complicated when being connected, and interfacial separation easily occurs during bending, is unfavorable for as the following flexible electronic device Power source.In contrast, the collector of plane supercapacitor, electrode, electrolyte, diaphragm are all on the same base, delay The segregative problem in bending process median surface has been solved, has been also easier to connect between device, has been conducive to construct high voltage, flexibility The supercapacitor of change.
The method for preparing plane supercapacitor at present mainly has the side such as photoetching, mask aided filter, laser writing Method, but have the shortcomings that be difficult to scale, at high cost.Based on this, the invention discloses one kind to prepare in any dielectric base The method of the plane supercapacitor of high voltage.Specially with containing electrode material, (graphene, carbon nanotube, fake capacitance are poly- Close object, metal oxide, metal hydroxides, metal sulfide, metal nitride etc.) dispersion liquid be ink, using printing Method, prepare the connector between the electrode, collector and capacitor of supercapacitor simultaneously in any dielectric base, one Step realizes the preparation and series connection of plane supercapacitor, obtained device high voltage and flexibility, can be used as wearable electronic device The power source of part, has broad application prospects.
Summary of the invention
The problems such as, step of connecting complexity low for voltage existing for supercapacitor, flexible difference, the present invention is intended to provide one The method that kind prepares the plane flexible super capacitor of high voltage in any dielectric base, to meet wearable electronic For the demand of power source.
In order to achieve the above objectives, the technical solution adopted by the present invention are as follows:
The plane supercapacitor of high voltage is prepared in any dielectric base, specifically includes the following steps:
(1) with the electrode material of supercapacitor, the additive and suitable dispersing agent for adjusting viscosity are raw material with guidance Electric ink prepares the electrode, collector and connection of supercapacitor using the method for printing simultaneously in any dielectric base Body.
(2) high tension super capacitor is prepared by cascaded structure design on a dielectric base, according to series connection monomer number Difference, adjust the output voltage of supercapacitor；
(3) electrolyte, fixture body fractionation sky are coated in electrode section, prepares high voltage plane supercapacitor.
Electrode material in the step (1) is graphene, carbon nanotube, fake capacitance polymer, metal oxide, metal One or more of hydroxide, metal sulfide, metal nitride.The graphene is electrochemical stripping graphite Alkene, chemical vapor deposition graphene, redox graphene, liquid phase removing graphene, organic synthesis graphene and containing graphene One or more of composite material；The carbon nanotube is one of single-walled carbon nanotube, multi-walled carbon nanotube Or two kinds；The fake capacitance polymer is polyaniline, polypyrrole, polythiophene, polyethylene dioxythiophene: in polystyrolsulfon acid It is one or more kinds of；The metal oxide is manganese dioxide, in ruthenium-oxide, iron oxide, cobalt oxide, molybdenum oxide, niobium oxide One or more；The metal hydroxides is one or both of cobalt hydroxide, nickel hydroxide, iron oxide hydroxide More than；The metal sulfide is one or both of molybdenum sulfide, cobalt sulfide；The metal nitride is vanadium nitride, nitridation One or both of niobium.
Additive is conductive black, sodium alginate, polytetrafluoroethylene (PTFE), carboxymethyl cellulose, butylbenzene rubber in the step (1) One or more of glue, polyvinyl chloride vinylacetate, Kynoar.
Dispersion liquid is water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, acetone, cyclohexanone, two in the step (1) One or more of methyl sulfoxide, dimethylbenzene, N,N-dimethylformamide, N-Methyl pyrrolidone, dibasic ester.It is excellent Selecting dispersion liquid is isopropanol, N,N-dimethylformamide, N-Methyl pyrrolidone, dibasic ester.
The dielectric base includes A4 paper, polyethylene terephthalate, nylon membrane, silk cloth, non-woven fabrics, glass Glass, surface have the mixing of one or more of silicon wafer of silicon dioxide layer.
In the step (1) printing process include inkjet printing, silk-screen printing, spraying printing, laser printing, in 3D printing One or more.
Electrode material concentration in ink is 0.01~100mg mL-1；The matter of the electrode material and additive Amount ratio is 0.5~50:1, and preferred scope is 5~30:1；The solid content of the ink is 0.1%~70%, and preferred scope exists 1%~50%.The graphene is having a size of 0.1~100 μm, and preferred scope is 1~10 μm, with a thickness of 0.7~5.0nm, preferably Range is 0.7~3nm.The carbon nanotube diameter be 0.5~100nm, preferred scope be 0.5~20nm, length be 0.1~ 300 μm, preferred scope is 1~100 μm.Electrode material concentration is 0.1~100mg mL in the graphene ink-1, preferred model It encloses for 1~10mg mL-1.Electrode material concentration is 0.1~100mg mL in the carbon nanotube ink-1, preferred scope be 1~ 10mg mL-1.The polyaniline, polypyrrole, polythiophene, polyethylene dioxythiophene: active material is dense in polystyrolsulfon acid ink Degree is 0.1~100mg mL-1, preferred scope is 1~10mg mL-1.The manganese dioxide, ruthenium-oxide, cobalt hydroxide, hydroxide Nickel, molybdenum oxide, molybdenum sulfide, cobalt sulfide, vanadium nitride, active material concentration is 0.1~100mg mL in niobium nitride ink-1, preferably Range is 1~5mg mL-1。
The graphene is having a size of 0.1~200 μm, with a thickness of 0.7~5.0nm；Carbon nanotube diameter be 0.5~ 100nm, length are 0.1~300 μm.
The electrode of the supercapacitor be line segment shape, bar shaped, interdigital, digital shape, alphabetical shape, in circular concentric One or more, the area of single electrode is at 10 μm2~20cm2, preferred scope 1mm2~1cm2；Electrode, collector and Body thickness is connected in 100nm~500 μm, preferred scope is 0.5~50 μm.
The difference of the series connection number of the supercapacitor, output voltage is adjustable between 1-10000V.
The two poles of the earth electrode material of the supercapacitor is identical or different；The supercapacitor obtained when electrode material is identical Referred to as symmetric form supercapacitor, the supercapacitor that material does not obtain simultaneously are known as asymmetrical type supercapacitor.
The electrode and connector of single supercapacitor are either straight line, is also possible to broken line or bending in described , be conducive to design device of different shapes, it is convenient integrated from different flexible wearable devices, adapt to the need of different scenes It asks.
The two poles of the earth electrode material of supercapacitor in the step (2) is identical or different.What is obtained when material is identical is super Grade capacitor is known as symmetric form supercapacitor, and the supercapacitor that material does not obtain simultaneously is known as asymmetrical type super capacitor Device.
Supercapacitor in the step (2), according to series connection number difference, output voltage can 1-10000V it Between adjust.
Electrolyte in the step (3) include water system (acid, alkalinity, neutral), organic system, ionic liquid system liquid, Gel and solid-state electrolytic solution, specially sulfuric acid solution, phosphoric acid solution, sodium hydroxide solution, potassium hydroxide solution, sodium sulphate are molten Liquid, sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, sodium sulphate/poly- second Enol, potassium chloride/polyacrylic acid potassium, sodium sulphate/polyacrylic acid potassium, sodium sulphate/polyvinylpyrrolidone, lithium perchlorate/poly- second Enol, 1- ethyl-3-methylimidazole hexafluorophosphate/Kynoar etc., preferably electrolyte be sulfuric acid/polyvinyl alcohol, phosphoric acid/ Polyvinyl alcohol, lithium chloride/polyvinyl alcohol, 1- ethyl-3-methylimidazole hexafluorophosphate/Kynoar.
A kind of integrated high voltage plane supercapacitor, the high voltage plane supercapacitor pass through multiple lists Only supercapacitor connects to obtain comprising the connection between multiple individual plane supercapacitors and supercapacitor Body；The independent plane supercapacitor has discontinuous patterned anode and cathode；Wherein, n supercapacitor When series connection respectively by the 1st anode and the 2nd cathode, the 2nd anode and the 3rd cathode ..., (n-1)th just Pole is connected with n-th of cathode by conduction connector；Wherein, the number of supercapacitor when n refers to series connection.
Advantages of the present invention:
1. the present invention realizes plane super capacitor electrode in any dielectric base previous step method using the method for printing The integration system of pole, collector and connector is standby and the series connection of multiple plane supercapacitors.
2. the plane supercapacitor output voltage with higher that the present invention produces, and by supercapacitor The control for number of connecting, the output voltage of adjustable supercapacitor.
3. the preparation method of the plane supercapacitor for the high voltage that the present invention produces is simple, low in cost, it is suitble to Carry out large-scale production.
4. the plane supercapacitor for the high voltage that the present invention produces uses stone compared to traditional supercapacitor The materials such as black alkene are used as collector, electrode active material and connector simultaneously, simplify device preparation, concatenated process flow, Also reduce the weight and volume of device itself.
5. the plane supercapacitor for the high voltage that the present invention produces has good flexibility, bending process is avoided The phenomenon that multiple solutions separation of middle appearance, power supply can be provided for flexible wearable electronic product.
6. the present invention in different dielectric bases, is manufactured that the plane supercapacitor of high voltage, but the present invention It is not limited only to the plane supercapacitor of high voltage, can be applied to the other energy storage devices of such as battery, also to prepare it He provides feasible scheme by the plane energy storage device of high voltage, has universality.
Detailed description of the invention
With reference to the accompanying drawing and embodiment the present invention is described in further detail:
What Fig. 1 made on glass is filled by the cyclic voltammetry curve and constant current of 4 concatenated devices of bar shaped supercapacitor Discharge curve.
What Fig. 2 made on PET is filled by the cyclic voltammetry curve and constant current of 10 concatenated devices of bar shaped supercapacitor Discharge curve.
Fig. 3 made on PET by the concatenated device schematic diagram of 130 bar shaped supercapacitors.
The cyclic voltammetry curve by 130 concatenated devices of bar shaped supercapacitor and constant current that Fig. 4 makes on PET Charging and discharging curve.
Specific embodiment
It elaborates combined with specific embodiments below to the method for the present invention, the present embodiment is before technical solution of the present invention It puts and is implemented, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
The graphene of intercalation stripping, conductive black are sufficiently mixed to obtain the two mixture with mass ratio 7:3, then passed through Said mixture is dispersed in the dibasic ester dissolved with polyvinyl chloride vinylacetate by ball-milling method, wherein mixture, polychlorostyrene second The mass ratio of alkene vinylacetate and dibasic ester is 1:1:9, electrically conductive ink of the dispersions obtained system as silk-screen printing.Design Screen printing screens, screen portion are 4 connectors between stripe device and device, and the length of stripe device single electrode is 1cm, width 0.6mm, spacing 1mm, connection body length are 6mm, width 4mm.When silk-screen printing, glass is placed in halftone At lower about 5mm, electrically conductive ink is coated in halftone one end blank space, and ink is then scraped net with the speed of about 3cm/s using scraper Glass is then dried 12h at 100 DEG C on glass by the version other end, the screen deposition that ink is squeezed through halftone therebetween, Phosphoric acid/polyvinyl alcohol gel electrolyte is finally coated at electrode.To get to 4 bar shaped super capacitors after liquid to be electrolysed solidification The concatenated device of device.
The electro-chemical test of Fig. 1 shows that the Tandem devices obtained on glass have ideal chemical property, and can be with The voltage of supercapacitor is improved by series connection.
Embodiment 2
The graphene of liquid phase removing, conductive black are sufficiently mixed with mass ratio 7:3 and uniformly obtain the two mixture, then Mixture is dispersed in the dibasic ester dissolved with polyvinyl chloride vinylacetate by ball-milling method, wherein mixture, polychlorostyrene second The mass ratio of alkene vinylacetate and dibasic ester is 1:1:9, the electrically conductive ink by dispersions obtained system as silk-screen printing.If Screen printing screens are counted, screen portion is the supercapacitor that 10 stripe devices are connected, stripe device single electrode Length is 1cm, width 0.6mm, spacing 1mm, and connection body length is 6mm, width 4mm.When silk-screen printing, PET is set Under halftone at about 5mm, electrically conductive ink is coated in halftone one end blank space, then using scraper with the speed of about 3cm/s by ink The halftone other end is scraped, then the screen deposition that ink is squeezed through halftone therebetween dries PET on PET at 100 DEG C 12h finally coats phosphoric acid/polyvinyl alcohol gel electrolyte, to get super to 10 bar shapeds after liquid solidification to be electrolysed at electrode The concatenated supercapacitor of capacitor.
The electro-chemical test of Fig. 2 shows that the integrated supercapacitor obtained on PET has good series connection behavior, The high voltage of output 8V can be stablized.Meanwhile the use of PET base further shows that this printing technology can be applied to not Same dielectric base
Embodiment 3
Redox graphene, conductive black are sufficiently mixed with mass ratio 9:1 and uniformly obtain mixture, then passes through ball Mixture is dispersed in the dibasic ester dissolved with polyvinyl chloride vinylacetate by mill method, wherein mixture, polyvinyl chloride acetic acid second The mass ratio of enester and dibasic ester is 1:1:9, the electrically conductive ink by dispersions obtained system as silk-screen printing.Design screen printing Brush halftone, screen portion are the supercapacitor that 130 stripe devices are connected, and the length of stripe device single electrode is 1cm, width 0.6mm, spacing 1mm, connection body length be 6mm, width 4mm, as shown in Figure 3.It, will when silk-screen printing PET is placed under halftone at about 5mm, and electrically conductive ink is coated in halftone one end blank space, then will with the speed of about 3cm/s using scraper Ink scrapes the halftone other end, and ink is squeezed through the screen deposition of halftone on PET therebetween, then by PET at 100 DEG C 12h is dried, phosphoric acid/polyvinyl alcohol gel electrolyte is finally coated at electrode, to get to by 130 after liquid solidification to be electrolysed The concatenated supercapacitor of stripe device, as shown in Figure 3.
What the electro-chemical test of Fig. 4 showed to obtain on PET is had by 130 concatenated supercapacitors of stripe device The output voltage of superelevation can be combined as its power source with the electronic device of high voltage is needed.
Embodiment 4
Multi-walled carbon nanotube, Kynoar are sufficiently mixed to obtain the two mixture with mass ratio 9:1, by mixture point It dissipates in N-Methyl pyrrolidone, the mass ratio of mixture and N-Methyl pyrrolidone is 1:8, regard dispersions obtained system as silk The electrically conductive ink of wire mark brush.Screen printing screens are designed, screen portion is the supercapacitor that 3 linear devices in series obtain, The length of linear device single electrode is 1cm, width 1mm, spacing 1mm, and connection body length is 6mm, width 1mm.Silk When wire mark brush, PET is placed under halftone at about 5mm, ink is coated in halftone one end blank space, then using scraper with about 3cm/s Speed ink is scraped into the halftone other end, ink is squeezed through the screen deposition of halftone on PET therebetween, then by PET Dry 12h at 100 DEG C, phosphoric acid/polyvinyl alcohol gel electrolyte finally coated at electrode, after liquid to be electrolysed solidification to get To by 3 concatenated supercapacitors of stripe device.The super electricity by 3 linear devices in series that electro-chemical test shows Container has the operating voltage of 2.4V.
Embodiment 5
Multi-walled carbon nanotube, Kynoar are sufficiently mixed to obtain the two mixture, mixture dispersion with mass ratio 9:1 In N-Methyl pyrrolidone, the mass ratio of mixture and N-Methyl pyrrolidone is 1:8, regard dispersions obtained system as silk screen The electrically conductive ink of printing.Screen printing screens are designed, screen portion is the supercapacitor that 3 concentric circles devices in series obtain, Concentric circles device inner circle radius is 4mm, and outer ring radius is 6mm, and spacing 2mm, connector is rectangle, length 1cm, width For 2mm.When silk-screen printing, nonwoven is arranged under halftone at about 5mm, ink is coated in halftone one end blank space, then using scraping Ink is scraped the halftone other end with the speed of about 3cm/s by knife, and ink is squeezed through the screen deposition of halftone in nonwoven therebetween On cloth, non-woven fabrics is then dried into 12h at 100 DEG C, 1- ethyl-3-methylimidazole tetrafluoro boric acid is finally coated at electrode Salt/Kynoar gel electrolyte, 100 DEG C of vacuum drying 12h are to get the super electricity arrived by 3 circular concentric devices in series Container.
Work electricity of the supercapacitor by 3 circular concentric devices in series that electro-chemical test shows with 7.5V Pressure, the supercapacitor for showing that printing obtains can be in different electrolyte kind steady operations.

Claims (14)

1.一种高电压平面型超级电容器的制备方法，具体包括以下步骤：1. a preparation method of a high-voltage planar supercapacitor, specifically comprising the following steps: (1)以超级电容器的电极材料，调节粘度的添加剂和分散剂为原料配制导电油墨，采用印刷的方法在任意绝缘基底上同时制备出超级电容器的电极、集流体和连接体；(1) Use the electrode material of the supercapacitor, the additive for adjusting the viscosity and the dispersant as the raw material to prepare the conductive ink, and use the printing method to simultaneously prepare the electrode, the current collector and the connector of the supercapacitor on any insulating substrate; (2)在绝缘基底上通过串联结构设计制备高电压超级电容器，根据串联单体个数的不同，调节超级电容器的输出电压；(2) A high-voltage supercapacitor is prepared by designing a series structure on an insulating substrate, and the output voltage of the supercapacitor is adjusted according to the difference in the number of series-connected monomers; (3)在电极部分涂覆电解液、连接体部分留空，制备出高电压平面型超级电容器。(3) Electrolyte is coated on the electrode part, and the connector part is left blank to prepare a high-voltage planar supercapacitor. 2.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述步骤(1)中的电极材料为石墨烯、碳纳米管、赝电容聚合物、金属氧化物、金属氢氧化物、金属硫化物、金属氮化物中的一种或两种以上。2. according to the preparation method of the high-voltage planar supercapacitor according to claim 1, it is characterized in that: the electrode material in described step (1) is graphene, carbon nanotube, pseudocapacitance polymer, metal oxide, One or more of metal hydroxides, metal sulfides, and metal nitrides. 3.根据权利要求2所述的高电压平面型超级电容器的制备方法，其特征在于：所述石墨烯为电化学剥离石墨烯、化学气相沉积石墨烯、还原氧化石墨烯、液相剥离石墨烯、有机合成石墨烯及含石墨烯的复合材料中的一种或两种以上；3. the preparation method of high-voltage planar supercapacitor according to claim 2, is characterized in that: described graphene is electrochemical stripping graphene, chemical vapor deposition graphene, reduced graphene oxide, liquid phase stripping graphene , one or more of organically synthesized graphene and graphene-containing composite materials; 所述碳纳米管为单壁碳纳米管、多壁碳纳米管中的一种或两种；The carbon nanotubes are one or both of single-walled carbon nanotubes and multi-walled carbon nanotubes; 所述赝电容聚合物为聚苯胺、聚吡咯、聚噻吩、聚乙烯二氧噻吩：聚苯乙烯磺酸中的一种或两种以上；The pseudocapacitive polymer is one or more of polyaniline, polypyrrole, polythiophene, polyethylene dioxythiophene: polystyrene sulfonic acid; 所述金属氧化物为二氧化锰、氧化钌、氧化铁、氧化钴、氧化钼、氧化铌中的一种或两种以上；The metal oxide is one or more of manganese dioxide, ruthenium oxide, iron oxide, cobalt oxide, molybdenum oxide, and niobium oxide; 所述金属氢氧化物为氢氧化钴、氢氧化镍、氢氧化氧铁中的一种或两种以上；The metal hydroxide is one or more of cobalt hydroxide, nickel hydroxide and iron oxyhydroxide; 所述金属硫化物为硫化钼、硫化钴中的一种或两种；The metal sulfide is one or both of molybdenum sulfide and cobalt sulfide; 所述金属氮化物为氮化钒、氮化铌中的一种或两种。The metal nitride is one or both of vanadium nitride and niobium nitride. 4.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述步骤(1)中添加剂为导电炭黑海藻酸钠、聚四氟乙烯、羧甲基纤维素、丁苯橡胶、聚氯乙烯醋酸乙烯酯、聚偏氟乙烯中的一种或两种以上。4. according to the preparation method of the high-voltage planar supercapacitor according to claim 1, it is characterized in that: in the described step (1), the additive is conductive carbon black sodium alginate, polytetrafluoroethylene, carboxymethyl cellulose, One or more of styrene-butadiene rubber, polyvinyl chloride acetate and polyvinylidene fluoride. 5.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述步骤(1)中分散液为水、甲醇、乙醇、异丙醇、正丁醇、乙二醇、丙酮、环己酮、二甲基亚砜、二甲苯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二价酸酯中的一种或两种以上。5. according to the preparation method of the high-voltage planar supercapacitor according to claim 1, it is characterized in that: in described step (1), dispersion liquid is water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol , one or more of acetone, cyclohexanone, dimethyl sulfoxide, xylene, N,N-dimethylformamide, N-methylpyrrolidone, and divalent acid esters. 6.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述的绝缘基底包括A4纸、聚对苯二甲酸乙二醇酯、尼龙膜、丝绸布、无纺布、玻璃、表面有二氧化硅层的硅片中的一种或两种以上混合。6. The method for preparing a high-voltage planar supercapacitor according to claim 1, wherein the insulating substrate comprises A4 paper, polyethylene terephthalate, nylon film, silk cloth, non-woven One or more of cloth, glass and silicon wafer with silicon dioxide layer on the surface are mixed. 7.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述步骤(1)中印刷方法包括喷墨打印、丝网印刷、喷涂打印、激光打印、3D打印中的一种或两种以上。7. according to the preparation method of the high-voltage planar supercapacitor of claim 1, it is characterized in that: in described step (1), printing method comprises ink jet printing, screen printing, spray printing, laser printing, 3D printing one or more of them. 8.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述的电极材料于油墨中浓度为0.01～100mg mL-1；所述电极材料与添加剂的质量比例为0.5～50：1；所述油墨的固含量为0.1％～70％。8. according to the preparation method of the high-voltage planar supercapacitor according to claim 1, it is characterized in that: the concentration of described electrode material in ink is 0.01～100mg mL -1 ; The mass ratio of described electrode material and additive is 0.5-50:1; the solid content of the ink is 0.1%-70%. 9.按照权利要求2所述的高电压平面型超级电容器的制备方法，其特征在于：所述的石墨烯尺寸为0.1～200μm，厚度为0.7～5.0nm；碳纳米管直径为0.5～100nm，长度为0.1～300μm。9 . The method for preparing a high-voltage planar supercapacitor according to claim 2 , wherein the graphene has a size of 0.1 to 200 μm, a thickness of 0.7 to 5.0 nm, and a carbon nanotube diameter of 0.5 to 100 nm. 10 . The length is 0.1 to 300 μm. 10.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述超级电容器的电极为线段形、条形、交叉指形、数字形、字母形、同心圆形中的一种或两种以上，单个电极的面积在10μm2～20cm2，电极、集流体和连接体厚度在100nm～500μm。10. The method for preparing a high-voltage planar supercapacitor according to claim 1, wherein the electrodes of the supercapacitor are in the shape of a line segment, a bar, an interdigital shape, a number shape, a letter shape, or a concentric circle. One or more of the two, the area of a single electrode is 10 μm 2 to 20 cm 2 , and the thickness of the electrode, the current collector and the connector is 100 nm to 500 μm. 11.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述超级电容器的串联个数的不同，其输出电压在1-10000V之间可调。11. The method for preparing a high-voltage planar supercapacitor according to claim 1, wherein the output voltage of the supercapacitor is adjustable between 1-10000V depending on the number of the supercapacitors connected in series. 12.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述超级电容器的两极电极材料相同或不同；电极材料相同时得到的超级电容器称为对称型超级电容器，材料不同时得到的超级电容器称为不对称型超级电容器。12. The preparation method of the high-voltage planar supercapacitor according to claim 1, characterized in that: the bipolar electrode materials of the supercapacitor are the same or different; the supercapacitor obtained when the electrode materials are the same is called a symmetric supercapacitor, The supercapacitors obtained with different materials are called asymmetrical supercapacitors. 13.按照权利要求1所述的高电压平面型超级电容器的制备方法，其特征在于：所述步骤(3)中电解液为硫酸溶液、磷酸溶液、氢氧化钠溶液、氢氧化钾溶液、硫酸钠溶液、硫酸/聚乙烯醇、磷酸/聚乙烯醇、氢氧化钾/聚乙烯醇、氯化锂/聚乙烯醇、氯化钾/聚丙烯酸钾，硫酸钠/聚丙烯酸钾，硫酸钠/聚乙烯吡咯烷酮，高氯酸锂/聚乙烯醇、硫酸钠/聚乙烯醇、1-乙基-3-甲基咪唑六氟磷酸盐/聚偏氟乙烯等中的一种或两种以上。13. according to the preparation method of the described high-voltage planar supercapacitor of claim 1, it is characterized in that: in described step (3), electrolyte is sulfuric acid solution, phosphoric acid solution, sodium hydroxide solution, potassium hydroxide solution, sulfuric acid Sodium solution, sulfuric acid/polyvinyl alcohol, phosphoric acid/polyvinyl alcohol, potassium hydroxide/polyvinyl alcohol, lithium chloride/polyvinyl alcohol, potassium chloride/potassium polyacrylate, sodium sulfate/potassium polyacrylate, sodium sulfate/polyvinyl alcohol Vinylpyrrolidone, one or more of lithium perchlorate/polyvinyl alcohol, sodium sulfate/polyvinyl alcohol, 1-ethyl-3-methylimidazolium hexafluorophosphate/polyvinylidene fluoride, etc. 14.一种采用权利要求1-13中任一方法制备的集成化高电压平面型超级电容器，其特征在于：所述高电压平面型超级电容器通过多个单独超级电容器串联得到，其包括多个单独的平面型超级电容器和超级电容器之间的连接体；所述单独平面型超级电容器具有不连续的图案化的正极和负极；其中，n个超级电容器串联时分别将第1个的正极和第2个的负极、第2个的正极和第3个的负极、…、第n-1个的正极和第n个的负极通过导电连接体相连；其中，n指串联时超级电容器的个数。14. An integrated high-voltage planar supercapacitor prepared by any of the methods of claims 1-13, wherein the high-voltage planar supercapacitor is obtained by connecting a plurality of individual supercapacitors in series, comprising a plurality of A single planar supercapacitor and a connector between the supercapacitors; the single planar supercapacitor has discontinuous patterned positive and negative electrodes; wherein, when n supercapacitors are connected in series, the positive and negative electrodes of the first are respectively connected. The two negative electrodes, the second positive electrode and the third negative electrode, ..., the n-1 positive electrode and the n negative negative electrode are connected by conductive connectors; where n refers to the number of supercapacitors in series.
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