CN104064361B - Self-charging super capacitor - Google Patents

Self-charging super capacitor Download PDF

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Publication number
CN104064361B
CN104064361B CN201310090472.6A CN201310090472A CN104064361B CN 104064361 B CN104064361 B CN 104064361B CN 201310090472 A CN201310090472 A CN 201310090472A CN 104064361 B CN104064361 B CN 104064361B
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China
Prior art keywords
ultracapacitor
electrode
charging
insulating barrier
nano friction
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CN201310090472.6A
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CN104064361A (en
Inventor
徐传毅
赵豪
吴宝荣
郝立星
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Nano New Energy Tangshan Co Ltd
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Nano New Energy Tangshan Co Ltd
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Priority to CN201310090472.6A priority Critical patent/CN104064361B/en
Priority to PCT/CN2014/070174 priority patent/WO2014146501A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G11/08—Structural combinations, e.g. assembly or connection, of hybrid or EDL capacitors with other electric components, at least one hybrid or EDL capacitor being the main component
    • 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

Abstract

The invention discloses a self-charging super capacitor which includes at least one nano friction generator which converts mechanical energy into electric energy, wherein each nano friction generator is provided with two output electrodes used for outputting electrical signals; a charging circuit module which is connected with the output electrodes of the at least one nano friction generator and used for carrying out adjustment and conversion on the electrical signals output by the nano friction generator; and a super capacitor which is connected with the charging circuit module and used for receiving and storing the electrical signals output by the charging circuit module. In the self-charging super capacitor, the nano friction generator plays a charging power supply role and converts mechanical energy into electric energy and then the charging circuit module carries out adjustment and conversion on the electrical signals and outputs the electrical signals to the super capacitor for storage so that self charging of the super capacitor is realized.

Description

Self-charging ultracapacitor
Technical field
The present invention relates to field of nanometer technology, more specifically to a kind of self-charging ultracapacitor.
Background technology
Ultracapacitor is also referred to as electrochemical capacitor, is a kind of electrochemistry storage between traditional capacitor and battery Can device.Compared with traditional capacitor, ultracapacitor possesses static capacity higher；Compared with battery, super capacitor utensil There is power density and overlength cycle life higher.Ultracapacitor combines the advantage of the two, is that one kind has a extensive future Energy storage device.
Existing ultracapacitor is mainly made up of electrode, electrolyte and barrier film.Wherein electrode includes electrode active material With colelctor electrode two parts.The effect of colelctor electrode is the internal resistance for reducing electrode, it is desirable to which it is big with electrode contact area, contact resistance It is small, and corrosion resistance is strong, stable performance in the electrolyte, and chemical reaction etc. does not occur.
Although performance of the supercapacitor is superior, the source of its charge power supply is single, it is impossible to realize self-charging, therefore it makes With generating certain limitation.Some ultracapacitors are there is also in the prior art, and they can be prepared to flexible structure, But preparation technology is complicated, it is difficult to be produced by large-scale processing.Ultracapacitor as a kind of future preferable energy-storage travelling wave tube, its Structure is also required to the design of uniqueness.Therefore, in order to preferably use and application ultracapacitor, urgent need to resolve above mentioned problem.
The content of the invention
Goal of the invention of the invention is directed to the defect of prior art, proposes a kind of self-charging ultracapacitor, not by External power source, realizes the self-charging of ultracapacitor.
The invention provides a kind of self-charging ultracapacitor, including：
At least one nano friction generator of electric energy is converted mechanical energy into, each nano friction generator has to be used for Export two output electrodes of electric signal；
It is being connected with the output electrode of at least one nano friction generator, by the nano friction generator output Electric signal be adjusted conversion charging circuit module；And
Electric signal be connected with the charging circuit module, receiving charging circuit module output is simultaneously stored Ultracapacitor.
Alternatively, the ultracapacitor includes：
Substrate；
Barrier film, ultracapacitor first electrode, ultracapacitor second electrode and the first collector in substrate, Second collector, the barrier film is arranged between the ultracapacitor first electrode and ultracapacitor second electrode, described First collector is connected with ultracapacitor first electrode, and second collector is connected with ultracapacitor second electrode, institute Charging circuit module is stated to be connected with first collector, the second collector；
Two bed course pieces on first collector and the second collector are located at respectively；
By described two bed course pieces, the barrier film, the ultracapacitor first electrode and ultracapacitor second electrode Electrolyte is filled with the cavity of formation, the cavity；
The encapsulated layer that the electrolyte is packaged.
Alternatively, at least one nano friction generator is arranged on the side of the ultracapacitor, it is described at least One nano friction generator shares the substrate with the ultracapacitor.
Alternatively, at least one nano friction generator sets up separately in the both sides of the ultracapacitor, is arranged on institute State at least one nano friction generator on the downside of ultracapacitor and share the substrate with the ultracapacitor, be arranged on institute State and be additionally provided with insulating barrier between at least one nano friction generator on the upside of ultracapacitor and the ultracapacitor.
Alternatively, the ultracapacitor includes：First collector of parallel stacking, ultracapacitor first successively Electrode, barrier film, ultracapacitor second electrode and the second collector and encapsulated layer；The charging circuit module and described first Collector, the connection of the second collector.
Alternatively, at least one nano friction generator is arranged on the side of the ultracapacitor, it is described at least Insulating barrier is additionally provided between one nano friction generator and the ultracapacitor.
Alternatively, at least one nano friction generator sets up separately in the both sides of the ultracapacitor, is arranged on institute State and the first insulation is additionally provided between at least one nano friction generator on the downside of ultracapacitor and the ultracapacitor Layer, is arranged between at least one nano friction generator on the upside of the ultracapacitor and the ultracapacitor and also sets up There is the second insulating barrier.
Alternatively, the nano friction generator has multiple, and array is arranged in same layer or different layers, is formed and is coupled Structure.
Alternatively, being arranged on the nano friction generator on the downside of the ultracapacitor has multiple, and array is arranged in together One layer or different layers, form parallel-connection structure；And/or, being arranged on the nano friction generator on the upside of the ultracapacitor has many It is individual, and array is arranged in same layer or different layers, forms parallel-connection structure.
Alternatively, the ultracapacitor is all-solid-state supercapacitor, selected from all solid state super electricity of symmetric form Graphene Container, all solid state symmetric form activity charcoal super capacitor, all solid state activated carbon and metal oxide asymmetric type supercapacitor, All solid state activated carbon mixes asymmetric with conducting polymer asymmetric type supercapacitor, all solid state activated carbon with lithium ion battery One kind in type ultracapacitor.
Alternatively, the material of the substrate is selected from the one kind in polyethylene terephthalate, silicon and silica.
Alternatively, the material of described two bed course pieces is selected from buna, butadiene-styrene rubber, nitrile rubber, butyl rubber, silicon One kind in rubber, polyurethane rubber, isoprene rubber, butadiene rubber, fluorubber and ACM.
Alternatively, the material of the barrier film is autoxidation graphite；Polyvinyl alcohol-sulfuric acid system；Polyvinyl alcohol-phosphoric acid body System；1- butyl, 3- methylimidazole bis trifluoromethyl sulphonyl sulfimide-fumed silica system；Polyaniline -1- ethyls, 3- methyl Tetrafluoroborate-trimethyl silanol system；1- butyl, 3- methyl imidazolium tetrafluoroborates-silica gel system；Polymethyl Sour methyl esters-ethylene carbonate-propene carbonate-lithium perchlorate system；Polymethyl methacrylate-ethylene carbonate-carbonic acid third Alkene ester-perchloric acid receives system；Polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium system；Polymethyl methacrylate-carbon One kind in vinyl acetate-propene carbonate-tetraethylammonium perchlorate's system.
Alternatively, the material of the encapsulated layer is aluminum plastic film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, propylene One kind in nitrile-BS, polymethyl methacrylate, polyformaldehyde, makrolon and PA membrane.
Alternatively, the material of first collector and the second collector is selected from the one kind in copper, silver, al and ni；It is described It is fine that the material of ultracapacitor first electrode and ultracapacitor second electrode is selected from Graphene, activated carbon, charcoal-aero gel, carbon One kind in dimension, metal oxide, conducting polymer and lithium ion battery electrode material.
Alternatively, the ultracapacitor first electrode and ultracapacitor second electrode are：Parallel construction, multiple row are parallel Structure, interdigital structure, serpentine configuration, helical structure, dendritic structure, spiral dendritic structure or dactylotype.
Alternatively, the charging circuit module includes：
It is being connected with the output electrode of at least one nano friction generator, by least one nano friction generator The electric signal of output carries out the rectification circuit module of rectification treatment；And
It is being connected with the rectification circuit module, by the rectification circuit module export unidirectional pulse direct current filtered Ripple treatment and obtain the filter circuit module of DC signal, the filter circuit module exports the DC signal to institute State ultracapacitor.
Alternatively, the charging circuit module also includes：Charge control module and switch/voltage changing module；
The charge control module is connected with filter circuit module, receives the direct current telecommunications of the filter circuit module output Number；The charge control module is connected with the ultracapacitor, receives the charging voltage of the ultracapacitor feedback；It is described Charge control module is connected with the switch/voltage changing module, and the charge control module is according to the DC signal and described Charging voltage obtains control signal, and the control signal is exported to the switch/voltage changing module；
Switch/the voltage changing module is connected with the filter circuit module, the direct current of wave reception filtering circuit module output Signal；Switch/the voltage changing module is connected with the ultracapacitor, and the switch/voltage changing module is according to the control letter for receiving Number carry out switching switching and export to described super after the DC signal to filter circuit module output carries out transformation treatment Level capacitor.
Alternatively, the charging circuit module also includes：Alternator control modules；The alternator control modules with it is described Ultracapacitor is connected, and receives the charging voltage of the ultracapacitor feedback；The alternator control modules and the nanometer Friction generator is connected, and the alternator control modules are exported to the nano friction generator according to the charging voltage and stopped The signal of generating.
Alternatively, the nano friction generator includes：The first electrode being cascading, the first high molecular polymer Insulating barrier, and second electrode；Wherein, the first electrode is arranged on the first side of the first high molecular polymer insulating barrier On surface；And the second side surface of the first high molecular polymer insulating barrier is set towards the second electrode, described first Electrode and second electrode constitute the output electrode of the nano friction generator.
Alternatively, the first high molecular polymer insulating barrier is provided with micro-nano structure towards the face of second electrode.
Alternatively, the nano friction generator is further included：It is arranged on the second electrode and first high score The second high molecular polymer insulating barrier between sub- polymer insulation layer, the second electrode is arranged on second polyphosphazene polymer On first side surface of compound insulating barrier；And the second side surface of the second high molecular polymer insulating barrier is high with described first Second side surface of Molecularly Imprinted Polymer insulating barrier is oppositely arranged.
Alternatively, the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier be oppositely arranged two At least one of individual face face is provided with micro-nano structure.
Alternatively, the nano friction generator is further included：It is arranged on the first high molecular polymer insulating barrier And the film layer between two parties between the second high molecular polymer insulating barrier, wherein, the film layer between two parties is thin polymer film Layer, and the face of the relatively described film layer between two parties of the first high molecular polymer insulating barrier and film layer is high relative to first between two parties On at least one of the face of the Molecularly Imprinted Polymer insulating barrier face and/or relatively described residence of the second high molecular polymer insulating barrier Between film layer face and film layer is provided with micro- with respect at least one of the face face of the second high molecular polymer insulating barrier between two parties Micro-nano structure.
Alternatively, the nano friction generator includes：The first electrode being cascading, the first high molecular polymer Insulating barrier, intervening electrode layer, the second high molecular polymer insulating barrier and second electrode；Wherein, the first electrode is arranged on On first side surface of the first high molecular polymer insulating barrier；The second electrode is arranged on second high molecular polymerization On first side surface of thing insulating barrier, the intervening electrode layer is arranged on the second side of the first high molecular polymer insulating barrier Between second side surface of surface and the second high molecular polymer insulating barrier, and the first high molecular polymer insulating barrier The face of relatively described intervening electrode layer and intervening electrode layer are relative at least in the face of the first high molecular polymer insulating barrier On individual face and/or the second high molecular polymer insulating barrier face of intervening electrode layer and intervening electrode layer relatively relative the At least one of the face of two high molecular polymer insulating barriers face is provided with micro-nano structure, the first electrode and second electrode phase Intervening electrode layer constitutes the output electrode of the nano friction generator described in Lian Houyu.
In the self-charging ultracapacitor that the present invention is provided, nano friction generator act as the role of charge power supply, It is exported to super electricity by converting mechanical energy into electric energy, then after electric power signal is adjusted into conversion by charging circuit module Container is stored, it is achieved thereby that the self-charging of ultracapacitor.
Brief description of the drawings
The theory structure block diagram of the self-charging ultracapacitor that Fig. 1 is provided for the present invention；
The dimensional structure diagram of the embodiment one of the self-charging ultracapacitor that Fig. 2 is provided for the present invention；
The schematic cross-section of the embodiment one of the self-charging ultracapacitor that Fig. 3 is provided for the present invention；
Fig. 4 a- Fig. 4 h illustrate for the vertical view of the structure between ultracapacitor first electrode and ultracapacitor second electrode Figure；
A kind of circuit theory schematic diagram of the embodiment one of the self-charging ultracapacitor that Fig. 5 is provided for the present invention；
Another circuit theory schematic diagram of the embodiment one of the self-charging ultracapacitor that Fig. 6 is provided for the present invention；
Fig. 7 shows that same layer is set up in parallel the schematic diagram of multiple nano friction generators；
The dimensional structure diagram of the embodiment two of the self-charging ultracapacitor that Fig. 8 is provided for the present invention；
The schematic cross-section of the embodiment two of the self-charging ultracapacitor that Fig. 9 is provided for the present invention；
The dimensional structure diagram of the embodiment three of the self-charging ultracapacitor that Figure 10 is provided for the present invention；
The schematic cross-section of the embodiment three of the self-charging ultracapacitor that Figure 11 is provided for the present invention；
The dimensional structure diagram of the example IV of the self-charging ultracapacitor that Figure 12 is provided for the present invention；
The schematic cross-section of the example IV of the self-charging ultracapacitor that Figure 13 is provided for the present invention；
Figure 14 a and Figure 14 b respectively illustrate the dimensional structure diagram of the first structure of nano friction generator and cut open Face structural representation；
Figure 15 a and Figure 15 b respectively illustrate the dimensional structure diagram of second structure of nano friction generator and cut open Face structural representation；
Figure 16 a and Figure 16 b respectively illustrate the dimensional structure diagram of the third structure of nano friction generator and cut open Face structural representation；
Figure 17 a and Figure 17 b respectively illustrate the 4th kind of dimensional structure diagram of structure of nano friction generator and cut open Face structural representation.
Specific embodiment
To be fully understood by purpose, feature and effect of the present invention, by following specific embodiments, the present invention is done in detail Describe in detail bright, but the present invention is not restricted to this.
The theory structure block diagram of the self-charging ultracapacitor that Fig. 1 is provided for the present invention.As shown in figure 1, the self-charging is super Level capacitor includes nano friction generator 11, charging circuit module 12 and ultracapacitor 13.Fig. 1 is only a schematic diagram, In practice, self-charging ultracapacitor can include one or more nano friction generators, each nano friction generator tool Have for exporting the two of electric signal output electrodes.The output electrode of nano friction generator 11 connects with charging circuit module 12 Connect, charging circuit module 12 is connected with ultracapacitor 13.The basic functional principle of the self-charging ultracapacitor is：In external force In the presence of, there is mechanical deformation in nano friction generator 11, convert mechanical energy into electric energy；Afterwards, nano friction generator 11 output electrode is by electric signal output to charging circuit module 12；The electric signal is adjusted conversion by charging circuit module 12 After export to ultracapacitor 13, ultracapacitor 13 receives the electric signal after regulation conversion and is stored, in case outside Electrical equipment is used.
In the self-charging ultracapacitor that the present embodiment is provided, nano friction generator act as the angle of charge power supply Color, it is by converting mechanical energy into electric energy, then is adjusted electric power signal by charging circuit module being exported to super after conversion Level capacitor is stored, it is achieved thereby that the self-charging of ultracapacitor.
The dimensional structure diagram of the embodiment one of the self-charging ultracapacitor that Fig. 2 is provided for the present invention.Such as Fig. 2 institutes Show, the self-charging ultracapacitor includes：One nanometer of ultracapacitor 21 and the side for being arranged on ultracapacitor 21 is rubbed Wipe generator 22.Wherein, nano friction generator 22 is placed in bottom, and ultracapacitor 21 is arranged on nano friction generator 22 Upper surface, nano friction generator 22 forms an entirety with ultracapacitor 21.Charging circuit module not shown in Fig. 2.Receive Two output electrodes of rice friction generator 22 are connected with charging circuit module, and charging circuit module connects with ultracapacitor 21 again Connect, so as to realize the storage of electric energy.
In the present embodiment, ultracapacitor 21 is all-solid-state supercapacitor, super selected from all solid state symmetric form Graphene Capacitor, all solid state symmetric form activity charcoal super capacitor, all solid state activated carbon and the asymmetric super capacitor of metal oxide Device, all solid state activated carbon mix non-with conducting polymer asymmetric type supercapacitor, all solid state activated carbon with lithium ion battery One kind in symmetric form ultracapacitor.Preferably, ultracapacitor 21 is selected from all solid state symmetric form Graphene ultracapacitor.
The schematic cross-section of the embodiment one of the self-charging ultracapacitor that Fig. 3 is provided for the present invention.With reference to Fig. 3, with complete The structure of ultracapacitor is illustrated as a example by solid-state symmetric form Graphene ultracapacitor.As shown in figure 3, ultracapacitor includes： Substrate 31, barrier film 32, ultracapacitor first electrode 33, ultracapacitor second electrode 34 and first in substrate 31 collect Fluid 35, the second collector 36, two bed course pieces 37, the cavity 38 filled with electrolyte, the encapsulation that electrolyte is packaged Layer 39.Its septation 32 is graphite oxide, and ultracapacitor first electrode 33 and ultracapacitor second electrode 34 are Graphene, First collector 35 and the second collector 36 are metal tape.Barrier film 32 is arranged on ultracapacitor first electrode 33 and super capacitor Between device second electrode 34, ultracapacitor first electrode 33 and ultracapacitor second electrode 34 are located at 32 liang of barrier film in Fig. 3 Side；First collector 35 is connected by conducting resinl with ultracapacitor first electrode 33, the second collector 36 by conducting resinl with Ultracapacitor second electrode 34 is connected, and the first collector 35 is located at the outside of ultracapacitor first electrode 33, second in Fig. 3 Collector 36 is located at the outside of ultracapacitor second electrode 34.Two bed course pieces 37 are provided with two collectors, by this Two bed course pieces 37, barrier film 32, ultracapacitor first electrode 33 and ultracapacitor second electrodes 34 are formed with cavity 38, use In filling electrolyte.Be packaged for electrolyte by encapsulated layer 39, so as to form very thin ultracapacitor.
Nano friction generator in figure 3 is layer structure, including：Friction electrode 30A, high molecular polymer insulating barrier 30B and electrode 30C.Wherein nano friction generator and ultracapacitor common base 31.The structure of the nano friction generator Will be described in detail later.
In the present embodiment, the material of substrate 31 is selected from polyethylene terephthalate (PET), silicon (Si) and silica (SiO2) in one kind.
The material of the first collector 35 and the second collector 36 is selected from the one kind in copper, silver, al and ni, specifically, in PVA Can be copper or silver etc. when system is as electrolyte, can be aluminium or nickel etc. when ionic liquid system is as electrolyte.
The material of ultracapacitor first electrode 33 and ultracapacitor second electrode 34 is selected from Graphene, activated carbon, charcoal One kind in aeroge, carbon fiber, metal oxide, conducting polymer and lithium ion battery electrode material.
The material of barrier film 32 can be selected from graphite oxide；PVA-H2SO4(polyvinyl alcohol-sulfuric acid) system；PVA-H3PO4It is (poly- Vinyl alcohol-phosphoric acid) system；1- butyl, 3- methylimidazole bis trifluoromethyl sulphonyl sulfimide-fumed silica system；PAN- [EMIm]BF4- TMS (polyaniline -1- ethyls, 3- methyl imidazolium tetrafluoroborates-trimethyl silanol) system；1- butyl, 3- first Base tetrafluoroborate-silica gel system；PMMA-EC-PC-LiClO4(polymethyl methacrylate-ethylene carbonate-carbonic acid Propylene-lithium perchlorate) system；PMMA-EC-PC-NaClO4(polymethyl methacrylate-ethylene carbonate-propylene carbonate Ester-perchloric acid is received) system；PEO-PEG-LiCF3SO3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system； PMMA-EC-PC-TEAClO4(polymethyl methacrylate-ethylene carbonate-propene carbonate-tetraethylammonium perchlorate) system In one kind.
Two materials of bed course piece 37 are selected from buna, butadiene-styrene rubber, nitrile rubber, butyl rubber, silicon rubber, poly- ammonia One kind in ester rubber, isoprene rubber, butadiene rubber, fluorubber and ACM.
Electrolyte is solid-state or colloidal state, and the system of electrolyte is PVA-H2SO4(polyvinyl alcohol-sulfuric acid) system；PVA- H3PO4(polyvinyl alcohol-phosphoric acid) system；1- butyl, 3- methylimidazole bis trifluoromethyl sulphonyl sulfimide-fumed silica system； PAN-[EMIm]BF4- TMS (polyaniline -1- ethyls, 3- methyl imidazolium tetrafluoroborates-trimethyl silanol) system；1- butyl, 3- methyl imidazolium tetrafluoroborates-silica gel system；PMMA-EC-PC-LiClO4(polymethyl methacrylate-ethylene carbonate- Propene carbonate-lithium perchlorate) system；PMMA-EC-PC-NaClO4(polymethyl methacrylate-ethylene carbonate-carbonic acid third Alkene ester-perchloric acid is received) system；PEO-PEG-LiCF3SO3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system； PMMA-EC-PC-TEAClO4(polymethyl methacrylate-ethylene carbonate-propene carbonate-tetraethylammonium perchlorate) system In one kind.
The material of encapsulated layer 39 is aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyformaldehyde (POM), poly- carbon One kind in acid esters (PC) and polyamide (PA).
In the present embodiment, the structure between ultracapacitor first electrode and ultracapacitor second electrode can have many Kind, Fig. 4 a- Fig. 4 h are the schematic top plan view of the structure between ultracapacitor first electrode and ultracapacitor second electrode.Figure 4a is illustrated that parallel construction, ultracapacitor first electrode 41A be with ultracapacitor second electrode 41B it is parallel, both Between be provided with barrier film 41C.Fig. 4 b are illustrated that many column parallel architectures, and wherein electrode 42A has multiple row and parallel to each other.Fig. 4 c show Be interdigital structure, barrier film 43C, Fig. 3 are provided between ultracapacitor first electrode 43A and ultracapacitor second electrode 43B Shown is exactly such interdigital structure.Fig. 4 d are illustrated that serpentine configuration, ultracapacitor first electrode 44A and super capacitor Barrier film is between device second electrode 44B.Fig. 4 e are illustrated that helical structure, ultracapacitor first electrode 45A and super Barrier film is between capacitor second electrode 45B.Fig. 4 f are illustrated that dendritic structure, ultracapacitor first electrode 46A and Barrier film is between ultracapacitor second electrode 46B.Fig. 4 g are illustrated that spiral dendritic structure, the electricity of ultracapacitor first Barrier film is between pole 47A and ultracapacitor second electrode 47B.Fig. 4 h are illustrated that dactylotype, ultracapacitor first Barrier film is between electrode 48A and ultracapacitor second electrode 48B.
Above-mentioned all solid state symmetric form Graphene ultracapacitor is preferably prepared using laser method, and its step includes：
(1) substrate (such as PET) is adhered on CD；
(2) by the graphite oxide aqueous solution (1-10mg/ml, the preparation method of graphite oxide is the Hummers methods for improving) drop It is coated onto in PET base, drying moisture leaves golden brown graphite oxide；
(3) above-mentioned CD is put on dvd CD writers, carries out structure fabrication, generate black graphene-structured；
(4) copper strips collector is pasted with conductive silver glue in graphene-structured both sides；
(5) the three-back-shaped bed course piece of sealing is placed on the basis of step (4)；
(6) gluey electrolyte is instilled in three-back-shaped bed course piece and moisture is evaporated；
(7) overall package obtains flexible solid electrolyte ultracapacitor.
Due to acting on the uncertainty of the external force size of nano friction generator so that what nano friction generator was produced Alternating current size does not know yet, such as：Single nano friction generator can export a few supreme kilovolts of volt under external force beating Voltage, this particularity requires that the reasonable design of external circuit reaches stabilization output.The present invention passes through charging circuit mould Block is adjusted conversion to the electric signal that nano friction generator is exported to realize stabilization output.
A kind of circuit theory schematic diagram of the embodiment one of the self-charging ultracapacitor that Fig. 5 is provided for the present invention.Fig. 5 shows The internal structure and itself and nano friction generator and the annexation of ultracapacitor of charging circuit module are gone out.Such as Fig. 5 Shown, charging circuit module includes：Rectification circuit module 51 and filter circuit module 52.Wherein, rectification circuit module 51 with extremely A few output electrode for nano friction generator is connected, and the electric signal that at least one nano friction generator is exported is carried out whole Stream process.Specifically, two inputs 51A and 51B of rectification circuit module 51 connect the two of nano friction generator 53 respectively Individual output electrode, receives the electric signal of the output of nano friction generator 53.For the structure including multiple nano friction generators, Two output electrodes of multiple nano friction generators are connected in parallel, then with two inputs of rectification circuit module 51 51A and 51B is connected.
Two output end 51C and 51D of rectification circuit module 51 are connected with filter circuit module 52, rectification circuit module 51 The electric signal that nano friction generator 53 is exported carries out the unidirectional pulse direct current electricity output obtained after rectification treatment to filtered electrical Road module 52.Filter circuit module 52 is connected with ultracapacitor 54, and filter circuit module 52 exports rectification circuit module 51 Unidirectional pulse direct current be filtered treatment and obtain DC signal and export to ultracapacitor 54.
As shown in figure 5, filter circuit module 52 has two ends.Specifically, the first end 52A of filter circuit module 52 with The output end 51D connections of rectification circuit module 51, the second end 52B of filter circuit module 52 and the output of rectification circuit module 51 End 51C connections.The first end 52A of filter circuit module 52 is connected with the first collector of ultracapacitor, filter circuit module 52 the second end 52B is connected with the second collector of ultracapacitor.In actual applications, the second end of filter circuit module 52 52B is typically grounded.
For the circuit shown in Fig. 5, when external force acts on nano friction generator, can occur nano friction generator Mechanical deformation, so as to produce the pulse electrical signal of exchange.The pulse electrical signal of this exchange first enters into rectification circuit module, leads to Over commutation circuit module carries out rectification to it, obtains the direct current unidirectionally pulsed.The direct current of this unidirectional pulsation inputs to filter again Wave circuit module is filtered, and the interference noise in the direct current of unidirectional pulsation is filtered, and obtains DC signal.Most Afterwards, this DC signal is directly inputted and charged to ultracapacitor.Here can be charged for a ultracapacitor, also may be used Think that the ultracapacitor of multiple parallel connections charges simultaneously.
The advantage of foregoing circuit is：(1) size and ultracapacitor electric capacity of electric energy are produced according to nano friction generator With the size of charging voltage, by the relevant parameter for adjusting filter circuit module, enabling rubbed using nanometer to greatest extent The electric energy produced by generator is wiped, energy conversion efficiency is improved；(2) according to the difference of applied environment, nano friction generator is produced Raw voltage amplitude scope is larger, can be adjusted to adapt to super by adjusting the relevant parameter of filter circuit module The voltage that capacitor charges, overcomes nano friction generator to produce the uncertainty of voltage swing.
Further, charging circuit module can also use a kind of structure being more highly preferred to.Fig. 6 for the present invention provides oneself Another circuit theory schematic diagram of the embodiment one of charge super capacitors.Fig. 6 shows preferred charging circuit module Internal structure and itself and nano friction generator and the annexation of ultracapacitor.As shown in fig. 6, charging circuit module is removed Include outside rectification circuit module 61 and filter circuit module 62, also including charge control module 63 and switch/voltage changing module 64.Wherein rectification circuit module 61 is connected with filter circuit module 62, specifically, rectification circuit module 61 respectively with filter circuit The first end 62A of module 62, the second end 62B of filter circuit module 62 are connected, rectification circuit module 61 and filter circuit module 62 function sees above, and repeats no more.
Charge control module 63 is connected with filter circuit module 62, the DC voltage letter of the output of wave reception filtering circuit module 62 Number U1, specifically, the first input end 63A of charge control module 63 is connected with the first end 62A of filter circuit module 62；Charge Control module 63 is connected with ultracapacitor 65, receive ultracapacitor 65 feedback charging voltage U, charging voltage U be The voltage signal formed between two collectors of ultracapacitor 65, specifically, the second input of charge control module 63 63B is connected with ultracapacitor 65；Charge control module 63 is also connected with switch/voltage changing module 64, specifically, charge control mould The output end 63C of block 63 is connected with the first end 64A of switch/voltage changing module 64, the first input end 63A of charge control module 63 It is connected with the second end 64B of switch/voltage changing module 64, charge control module 63 is according to d. c. voltage signal U1 and charging voltage U Control signal is obtained, to the output control signal of switch/voltage changing module 64.Switch/voltage changing module 64 connects with filter circuit module 62 Connect, wave reception filtering circuit module 62 output d. c. voltage signal U1, specifically, the second end 64B of switch/voltage changing module 64 and The first end 62A connections of filter circuit module 62；Switch/voltage changing module 64 is also connected with ultracapacitor 65, specifically, opens 3rd end 64C of pass/voltage changing module 64 is connected with ultracapacitor 65, and switch/voltage changing module 64 is according to the control signal for receiving Carry out switching switching and the d. c. voltage signal to the output of filter circuit module 62 is adjusted treatment, be adjusted to adapt to super The voltage U2 that capacitor 65 charges.
For the circuit shown in Fig. 6, it is input into from the d. c. voltage signal U1 that obtains unlike Fig. 5, is processed after filtering To charge control module 63, when charge control module 63 can be determined to super according to the size of this d. c. voltage signal U1 Capacitor 65 charges；And the charge condition of ultracapacitor 65 is paid close attention to, according to the shape that ultracapacitor 65 charges Condition carrys out controlling switch/voltage changing module 64.The output voltage of circuit module 62 is an output voltage for incrementally increasing after filtering, Until increasing to pressure limiting voltage, this pressure limiting voltage is a circuit protection voltage to this output voltage, prevents circuit because voltage mistake It is high and damage.
Because whole charging circuit module is no external power supply, 63 controlling switches of charge control module/voltage changing module 64 working powers charged to ultracapacitor 65 also come from nano friction generator electricity, therefore specially in control of charging Molding block 63 sets a startup voltage, after the output voltage of filter circuit module 62 reaches the startup voltage, charge control The ability driving switch of module 63/voltage changing module 64 starts charging.
Another effect of charge control module 63 be according to the size of d. c. voltage signal U1 for obtaining after filtering and The size of the charging voltage U of ultracapacitor 65, is adjusted to d. c. voltage signal U1, is adjusted to adaptation ultracapacitor 65 and fills The voltage U2 of electricity, and selective driving switch/voltage changing module 64 charges to ultracapacitor 65.
It can be seen from C=Q/U, the capacity C of ultracapacitor is a fixed value, in the process charged to ultracapacitor In, quantity of electric charge Q is being continuously increased, and the voltage U of ultracapacitor is also constantly rising therewith.In order to more effectively give super capacitor Device charges, what the charging voltage U and filter circuit module 62 that charge control module 63 is fed back according to ultracapacitor 65 were exported The numerical information of d. c. voltage signal U1 adjusts the circuit in switch/voltage changing module 64, and realization turns to voltage U1 to U2 Change, obtain the real time charging voltage U2 of ultracapacitor 65.There is a corresponding charging matching relationship between U2 and U, to ensure Highest energy conversion efficiency.As an example it is assumed that ultracapacitor 65 is U0 full of voltage, charge control module 63 will be super Level capacitor 65 feedback charging voltage U and U0 be compared, if U be less than U0, show ultracapacitor 65 and also underfill, it is necessary to Continue to charge；If U is equal to U0, show that ultracapacitor 65 has been filled with.Meanwhile, charge control module 63 is also by filter circuit module The d. c. voltage signal U1 of 62 outputs compares with U0, if U1 is more than U0, the control of the output control signal of charge control module 63 is opened Pass/voltage changing module 64 carries out step-down treatment to U1, obtains the real time charging voltage U2 of ultracapacitor 65；If U1 is less than U0, The output control signal controlling switch of charge control module 63/voltage changing module 64 carries out boosting treatment to U1, obtains ultracapacitor 65 real time charging voltage U2.
Here can be charged for a ultracapacitor, or multiple ultracapacitors charge, and such as Fig. 6 shows Three ultracapacitors, these three ultracapacitors are connected in parallel.When being charged for multiple ultracapacitors, can fill one by one It is full, it is also possible to be simultaneously filled with.It is full of one by one and is achieved in the following ways：Charge control module 63 currently will charge The charging voltage U of ultracapacitor feedback is full of voltage U0 and is compared with it, if U has reached U0, then charge control Switch is switched to next ultracapacitor by the output control signal controlling switch of module 63/voltage changing module 64, is continued as next Individual ultracapacitor is charged.
Further, in order to protect nano friction generator, charging circuit module can also include alternator control modules 66.The alternator control modules 66 are connected with ultracapacitor 65, receive the charging voltage U of the feedback of ultracapacitor 65, and this fills Piezoelectric voltage U is the voltage signal formed between two collectors of ultracapacitor 65；Alternator control modules 66 also with receive Rice friction generator connection, to the signal that nano friction generator output stops generating electricity.When ultracapacitor 65 is full of, can obtain Voltage is full of to one, alternator control modules 66 should be fed back to full of voltage, and then alternator control modules 66 can rub nanometer Wipe generator to close, so as to stop generating electricity.
The advantage of the circuit shown in Fig. 6 is：(1) due to act on nano friction generator external force size it is uncertain, So that the alternating current size that nano friction generator is produced does not know yet, uncertain magnitude of voltage can be converted into being adapted to by this circuit The magnitude of voltage that ultracapacitor charges, strong adaptability extends the application field of self-charging ultracapacitor；(2) due to circuit In be specifically designed charge control module, the real-time voltage according to ultracapacitor adjusts its charging voltage, makes super capacitor The real-time voltage of device maintains a Dynamic Matching relation with charging voltage, has reached the electric energy for sending nano friction generator Fill to greatest extent and give ultracapacitor, realize the energy storage effect of maximum；(3) being full of according to ultracapacitor, generates electricity Whether machine control module control nano friction generator works, and then extends the service life of nano friction generator；(4) when for When multiple ultracapacitors are charged, when one of them is full of, next ultracapacitor can be automatically switched to and charged.
The self-charging ultracapacitor that the present embodiment is provided is not limited only to include single nano friction generator, in super electricity The side of container can also set multiple nano friction generators.Specifically, the nanometer for being arranged on ultracapacitor side is rubbed Wiping generator has multiple, and these nano friction generator arrays are arranged in same layer or different layers, their corresponding output electrodes It is joined together to form parallel-connection structure.Its arrangement can refer to Fig. 7., electricity larger with the voltage of single nano friction generator generation Flow less feature to compare, multiple nano friction generators of parallel connection can increase the output of electric current, reach and preferably fill Electric effect；And because multiple nano friction generators are evenly distributed, its uniform force can be made, imitated with good linear superposition Really.
The dimensional structure diagram of the embodiment two of the self-charging ultracapacitor that Fig. 8 is provided for the present invention.Such as Fig. 8 institutes Show, the self-charging ultracapacitor includes：Ultracapacitor 81 and the nano friction set up separately in the both sides of ultracapacitor 81 generate electricity Machine 82 and 83, is similar to " sandwich " structure.Wherein, nano friction generator 82 is arranged on the downside of ultracapacitor 81, Nano friction generator 83 is arranged on the upside of ultracapacitor 81.Ultracapacitor 81 generates electricity with the nano friction of upper and lower both sides Machine 82 and 83 forms an entirety.Charging circuit module not shown in Fig. 8.Respective two of nano friction generator 82 and 83 is defeated Go out electrode and be connected in parallel and be connected with charging circuit module, charging circuit module connects with two collectors of ultracapacitor 81 again Connect, so as to realize the storage of electric energy.
In the present embodiment, ultracapacitor 81 is all-solid-state supercapacitor, super selected from all solid state symmetric form Graphene Capacitor, all solid state symmetric form activity charcoal super capacitor, all solid state activated carbon and the asymmetric super capacitor of metal oxide Device, all solid state activated carbon mix non-with conducting polymer asymmetric type supercapacitor, all solid state activated carbon with lithium ion battery One kind in symmetric form ultracapacitor.Preferably, ultracapacitor 81 is selected from all solid state symmetric form Graphene ultracapacitor.
The schematic cross-section of the embodiment two of the self-charging ultracapacitor that Fig. 9 is provided for the present invention.As shown in figure 9, super Level capacitor 81 structure it is identical with described by embodiment one, the available material of device that it is included also with embodiment one Described is identical, will not be repeated here.Nano friction generator 82 and 83 is layer structure, will be described in detail later. Nano friction generator 82 and the common base of ultracapacitor 81, also set between nano friction generator 83 and ultracapacitor 81 It is equipped with insulating barrier 90.Herein it should be noted that when nano friction generator and during ultracapacitor common base, without plus it is exhausted Edge layer, when nano friction generator and ultracapacitor do not have common base, it is necessary to plus insulating barrier, prevent conducting.
Charging circuit module is also identical with described in embodiment one in the present embodiment, will not be repeated here.
The self-charging ultracapacitor that the present embodiment is provided is not limited only to include upper and lower two nano friction generators, super The upside and/or downside of level capacitor can set multiple nano friction generators, specifically, specifically, be arranged on super Nano friction generator on the downside of level capacitor can have multiple, and array is arranged in same layer or different layers, is formed and is coupled Structure；And/or, being arranged on the nano friction generator on the upside of ultracapacitor can have a multiple, and array be arranged in same layer or Different layers, form parallel-connection structure.Its arrangement can refer to Fig. 7.Multiple nano friction generators of parallel connection can increase electric current Output, reach more preferable charging effect；And because multiple nano friction generators are evenly distributed, its uniform force can be made, With good linear superposition effect.
The dimensional structure diagram of the embodiment three of the self-charging ultracapacitor that Figure 10 is provided for the present invention.Such as Figure 10 institutes Show, the self-charging ultracapacitor includes：Ultracapacitor 101 rubs with a nanometer for being arranged on the side of ultracapacitor 101 Generator 102 is wiped, insulating barrier 103 is additionally provided between nano friction generator 102 and ultracapacitor 101.Wherein, nano friction Generator 102 is placed in bottom, and insulating barrier 103 is located at the upper surface of nano friction generator 102, and ultracapacitor 101 is located at exhausted The upper surface of edge layer 103.Ultracapacitor 101, insulating barrier 103 and nano friction generator 102 form an entirety.In Figure 10 Not shown charging circuit module.Two output electrodes of nano friction generator 102 are connected with charging circuit module, charging circuit Module is connected with two collectors of ultracapacitor 101 again, so as to realize the storage of electric energy.
In the present embodiment, ultracapacitor 101 is all-solid-state supercapacitor, super selected from solid symmetrical kenel Graphene entirely Capacitor, all solid state symmetric form activity charcoal super capacitor, all solid state activated carbon and the asymmetric super capacitor of metal oxide Device, all solid state activated carbon mix non-with conducting polymer asymmetric type supercapacitor, all solid state activated carbon with lithium ion battery One kind in symmetric form ultracapacitor.Preferably, ultracapacitor 101 is selected from all solid state symmetric form Graphene super capacitor Device.
The schematic cross-section of the embodiment three of the self-charging ultracapacitor that Figure 11 is provided for the present invention.As shown in figure 11, Ultracapacitor includes：Successively the first collector 111 of parallel stacking, ultracapacitor first electrode 112, barrier film 113, The collector 115 of ultracapacitor second electrode 114 and second, in addition ultracapacitor (do not show in Figure 11 including encapsulated layer also Go out).Insulating barrier 103 is connected with the contact of the first collector 111.Nano friction generator 102 in Figure 11 is layer structure, its tool Body structure will be described in detail later.
In the present embodiment, the material of the first collector 111 and the second collector 115 is selected from copper, silver, al and ni Kind.
The material of ultracapacitor first electrode 112 and ultracapacitor second electrode 114 be selected from Graphene, activated carbon, One kind in charcoal-aero gel, carbon fiber, metal oxide, conducting polymer and lithium ion battery material.
The material of barrier film 113 can be selected from graphite oxide；PVA-H2SO4(polyvinyl alcohol-sulfuric acid) system；PVA-H3PO4 (polyvinyl alcohol-phosphoric acid) system；1- butyl, 3- methylimidazole bis trifluoromethyl sulphonyl sulfimide-fumed silica system；PAN- [EMIm]BF4- TMS (polyaniline -1- ethyls, 3- methyl imidazolium tetrafluoroborates-trimethyl silanol) system；1- butyl, 3- first Base tetrafluoroborate-silica gel system；PMMA-EC-PC-LiClO4(polymethyl methacrylate-ethylene carbonate-carbonic acid Propylene-lithium perchlorate) system；PMMA-EC-PC-NaClO4(polymethyl methacrylate-ethylene carbonate-propylene carbonate Ester-perchloric acid is received) system；PEO-PEG-LiCF3SO3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system； PMMA-EC-PC-TEAClO4(polymethyl methacrylate-ethylene carbonate-propene carbonate-tetraethylammonium perchlorate) system In one kind.
Electrolyte is solid-state or colloidal state, and the system of electrolyte is PVA-H2SO4(polyvinyl alcohol-sulfuric acid) system；PVA- H3PO4(polyvinyl alcohol-phosphoric acid) system；1- butyl, 3- methylimidazole bis trifluoromethyl sulphonyl sulfimide-fumed silica system； PAN-[EMIm]BF4- TMS (polyaniline -1- ethyls, 3- methyl imidazolium tetrafluoroborates-trimethyl silanol) system；1- butyl, 3- methyl imidazolium tetrafluoroborates-silica gel system；PMMA-EC-PC-LiClO4(polymethyl methacrylate-ethylene carbonate- Propene carbonate-lithium perchlorate) system；PMMA-EC-PC-NaClO4(polymethyl methacrylate-ethylene carbonate-carbonic acid third Alkene ester-perchloric acid is received) system；PEO-PEG-LiCF3SO3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system； PMMA-EC-PC-TEAClO4(polymethyl methacrylate-ethylene carbonate-propene carbonate-tetraethylammonium perchlorate) system In one kind.
The material of encapsulated layer is aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyformaldehyde (POM), poly- carbon One kind in acid esters (PC) and polyamide (PA).
Charging circuit module is also identical with described in embodiment one in the present embodiment, will not be repeated here.Charge electricity Road module is connected with the collector 115 of above-mentioned first collector 111 and second.
The self-charging ultracapacitor that the present embodiment is provided is not limited only to include single nano friction generator, in super electricity The side of container can also set multiple nano friction generators specifically, be arranged on the nano friction of ultracapacitor side Generator has multiple, and these nano friction generator arrays are arranged in same layer or different layers, and their corresponding output electrodes connect It is connected together to form parallel-connection structure.Its arrangement can refer to Fig. 7., electric current larger with the voltage of single nano friction generator generation Less feature is compared, and multiple nano friction generators of parallel connection can increase the output of electric current, reaches preferably charging Effect；And because multiple nano friction generators are evenly distributed, its uniform force can be made, imitated with good linear superposition Really.
The dimensional structure diagram of the example IV of the self-charging ultracapacitor that Figure 12 is provided for the present invention.Such as Figure 12 institutes Show, the self-charging ultracapacitor includes：Ultracapacitor 121 and the nano friction set up separately in the both sides of ultracapacitor 121 are sent out Motor 122 and 123.Wherein, nano friction generator 122 is arranged on the downside of ultracapacitor 121, nano friction generator The first insulating barrier 124 is additionally provided between 122 and ultracapacitor 121；Nano friction generator 123 is arranged on ultracapacitor 121 upside, is additionally provided with the second insulating barrier 125 between nano friction generator 123 and ultracapacitor 121.Ultracapacitor 121 with the nano friction generator 122,123 and the first insulating barrier 124 of upper and lower both sides, the second insulating barrier 125 formed one it is whole Body.Charging circuit module not shown in Figure 12.Respective two output electrodes of nano friction generator 122 and 123 are connected in parallel on one Rise and be connected with charging circuit module, charging circuit module is connected with two collectors of ultracapacitor 121 again, so as to realize electricity The storage of energy.
In the present embodiment, ultracapacitor 121 is all-solid-state supercapacitor, super selected from all solid state symmetric form Graphene Capacitor, all solid state symmetric form activity charcoal super capacitor, all solid state activated carbon and the asymmetric super capacitor of metal oxide Device, all solid state activated carbon mix non-with conducting polymer asymmetric type supercapacitor, all solid state activated carbon with lithium ion battery One kind in symmetric form ultracapacitor.Preferably, ultracapacitor 121 is selected from all solid state symmetric form Graphene super capacitor Device.
The schematic cross-section of the example IV of the self-charging ultracapacitor that Figure 13 is provided for the present invention.As shown in figure 13, The structure of ultracapacitor 121 is identical with described by embodiment three, the available material of device that it is included also with implementation It is identical described by example three, will not be repeated here.Nano friction generator 122 and 123 is layer structure, will in detail below Explanation.The first insulating barrier 124, nano friction generator are provided between nano friction generator 122 and ultracapacitor 121 The second insulating barrier 125 is provided between 123 and ultracapacitor 121.
Charging circuit module is also identical with described in embodiment one in the present embodiment, will not be repeated here.
The self-charging ultracapacitor that the present embodiment is provided is not limited only to include upper and lower two nano friction generators, super The upside and/or downside of level capacitor can set multiple nano friction generators, specifically, be arranged under ultracapacitor The nano friction generator of side can have multiple, and array is arranged in same layer or different layers, form parallel-connection structure；And/or, if Putting the nano friction generator on the upside of ultracapacitor can have multiple, and array is arranged in same layer or different layers, be formed Parallel-connection structure.Its arrangement can refer to Fig. 7.Multiple nano friction generators of parallel connection can increase the output of electric current, reach More preferable charging effect；And because multiple nano friction generators are evenly distributed, its uniform force can be made, with good line Property Overlay.
The structure and operation principle of the nano friction generator in self-charging ultracapacitor is described in detail below.
The first structure of nano friction generator is as shown in Figure 14 a and Figure 14 b.Figure 14 a and Figure 14 b are respectively illustrated and received The dimensional structure diagram and cross-sectional view of the first structure of rice friction generator.The nano friction generator bag Include：The first electrode 141 being cascading, the first high molecular polymer insulating barrier 142, and second electrode 143.Specifically Ground, first electrode 141 is arranged on the first side surface of the first high molecular polymer insulating barrier 142；And first high molecular polymerization Second side surface of thing insulating barrier 142 is felt with the surface contact friction of second electrode 143 and at second electrode and first electrode Electric charge should be gone out.Therefore, above-mentioned first electrode 141 and second electrode 143 constitute two output electrodes of nano friction generator.
In order to improve the generating capacity of nano friction generator, in the second side of the first high molecular polymer insulating barrier 142 Surface (on the face i.e. with respect to second electrode 143) is further provided with micro-nano structure 144.Therefore, when nano friction generator is subject to During extruding, the first high molecular polymer insulating barrier 142 can better contact with friction with the apparent surface of second electrode 143, and More electric charge is induced at first electrode 141 and second electrode 143.Due to above-mentioned second electrode 143 be mainly used in First high molecular polymer insulating barrier 142 rubs, therefore, second electrode 143 can also be referred to as friction electrode.
Above-mentioned micro-nano structure 144 can specifically take the possible implementation of the following two kinds：First way is that this is micro- Micro-nano structure is micron order or nano level very small concaveconvex structure.The concaveconvex structure can increase frictional resistance, improve and generate electricity Efficiency.The concaveconvex structure can directly be formed in film preparation, it is also possible to make the first high molecular polymerization with the method for polishing The surface of thing insulating barrier forms irregular concaveconvex structure.Specifically, the concaveconvex structure can be semicircle, striated, cube The concaveconvex structure of the shapes such as build, rectangular pyramid or cylinder.The second way is that the micro-nano structure is the poroid knot of nanoscale Structure, now the first high molecular polymer insulating barrier material therefor be preferably Kynoar (PVDF), its thickness is 0.5-1.2mm (preferably 1.0mm), and it is provided with multiple nano-pores with respect to the face of second electrode.Wherein, the size of each nano-pore, i.e. width And depth, can be according to being selected the need for application, the size of preferred nano-pore is：Width is 10-100nm and depth It is 4-50 μm.The quantity of nano-pore can be as needed output current value and magnitude of voltage be adjusted, preferred these nanometers Hole is pitch of holes for 2-30 μm is uniformly distributed, and preferred average pitch of holes is 9 μm and is uniformly distributed.
Lower mask body introduces the operation principle of the nano friction generator shown in Figure 14 a and Figure 14 b.When the nanometer is rubbed When each layer for wiping generator is bent downwardly, the high molecular polymer of second electrode 143 and first insulation in nano friction generator The surface phase mutual friction of layer 142 produces electrostatic charge, and the generation of electrostatic charge can make the electricity between first electrode 141 and second electrode 143 Appearance changes, so as to cause electrical potential difference occur between first electrode 141 and second electrode 143.Due to first electrode 141 and Two electrodes 143 are connected as the output electrode of nano friction generator with charging circuit module, and then are connected with ultracapacitor, Charging circuit module and ultracapacitor constitute the external circuit of nano friction generator, two output electricity of nano friction generator Connected equivalent to by external circuit between pole.When each layer of the nano friction generator returns to original state, at this moment it is formed in Built-in potential between first electrode and second electrode disappears, and will now be produced again between Balanced first electrode and second electrode The reverse electrical potential difference of life.By rubbing repeatedly and recovering, it is possible to form periodic ac signal in external circuit.The friendship By being converted to DC signal after charging circuit module treatment, the DC signal is exported and entered stream electric signal to ultracapacitor Row storage, it is achieved thereby that the self-charging of ultracapacitor.
Research discovery according to inventor, metal and high molecular polymer friction, metal are more easy to lose electronics, therefore use Metal electrode can improve energy output with high molecular polymer friction.Therefore, correspondingly, in receiving shown in Figure 14 a and Figure 14 b In rice friction generator, second electrode is rubbed as friction electrode (i.e. metal) due to needing with the first high molecular polymer Wipe, thus its material can be selected from metal or alloy, wherein metal can be Au Ag Pt Pd, aluminium, nickel, copper, titanium, chromium, selenium, Iron, manganese, molybdenum, tungsten or vanadium；Alloy can be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel Alloy, metal, tin alloy, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy. First electrode due to that need not be rubbed, therefore, except can select the above-mentioned second electrode enumerated material in addition to, other The material that electrode can be made can also be applied, that is to say, that first electrode is except that can be selected from metal or alloy, wherein metal Can be Au Ag Pt Pd, aluminium, nickel, copper, titanium, chromium, selenium, iron, manganese, molybdenum, tungsten or vanadium；Alloy can be aluminium alloy, titanium alloy, Magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, tin alloy, cadmium alloy, bismuth alloy, indium alloy, Outside gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy, indium tin oxide, Graphene, nano silver wire are also selected from The nonmetallic materials such as film.
Second structure of nano friction generator is as shown in Figure 15 a and Figure 15 b.Figure 15 a and Figure 15 b are respectively illustrated and received The dimensional structure diagram and cross-sectional view of second structure of rice friction generator.The nano friction generator bag Include：The first electrode 151 being cascading, the first high molecular polymer insulating barrier 152, the second high molecular polymer insulating barrier 154 and second electrode 153.Specifically, first electrode 151 is arranged on the first side of the first high molecular polymer insulating barrier 152 On surface；Second electrode 153 is arranged on the first side surface of the second high molecular polymer insulating barrier 154；Wherein, the first high score Second side surface of sub- polymer insulation layer 152 contacts friction with the second side surface of the second high molecular polymer insulating barrier 154 And induce electric charge at first electrode 151 and second electrode 153.Wherein, first electrode 151 and second electrode 153 are constituted and received Two output electrodes of rice friction generator.
In order to improve the generating capacity of nano friction generator, the first high molecular polymer insulating barrier 152 and the second high score At least one of two faces that sub- polymer insulation layer 154 is oppositely arranged face is provided with micro-nano structure.In Figure 15 b, first The face of high molecular polymer insulating barrier 152 is provided with micro-nano structure 155.Therefore, when nano friction generator is squeezed, the One high molecular polymer insulating barrier 152 can be better contacted with the apparent surface of the second high molecular polymer insulating barrier 154 and rubbed Wipe, and more electric charge is induced at first electrode 151 and second electrode 153.Above-mentioned micro-nano structure can refer to above Description, here is omitted.
The operation principle of the nano friction generator shown in Figure 15 a and Figure 15 b is rubbed with the nanometer shown in Figure 14 a and Figure 14 b The operation principle for wiping generator is similar to.Differ only in, when each layer of the nano friction generator shown in Figure 15 a and Figure 15 b is curved Qu Shi, is come with the surface phase mutual friction of the second high molecular polymer insulating barrier 154 by the first high molecular polymer insulating barrier 152 Produce electrostatic charge.Accordingly, with respect to the operation principle of the nano friction generator shown in Figure 15 a and Figure 15 b, here is omitted.
Mainly by polymer, (the first high molecular polymer insulate nano friction generator shown in Figure 15 a and Figure 15 b Layer) friction and polymer (the second high molecular polymer insulating barrier) between produces electric signal.
In this configuration, first electrode and second electrode material therefor can be indium tin oxide, Graphene, silver nanoparticle Line film, metal or alloy, wherein metal can be Au Ag Pt Pd, aluminium, nickel, copper, titanium, chromium, selenium, iron, manganese, molybdenum, tungsten or vanadium； Alloy can be aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, metal, tin conjunction Gold, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.
In above two structure, the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier are respectively selected from Kapton, aniline-formaldehyde resin film, polyformaldehyde film, ethyl cellulose film, polyamide film, melamine first Aldehyde film, polyethylene glycol succinate film, cellophane, cellulose acetate film, polyethylene glycol adipate film, Polydiallyl phthalate film, fiber (regeneration) sponge films, elastic polyurethane body thin film, styrene-acrylonitrile copolymer copolymer Film, styrene-butadiene-copolymer film, staple fibre film, poly- methyl film, methacrylic acid ester film, polyvinyl alcohol Film, polyvinyl alcohol film, polyester film, polyisobutene film, polyurethane flexible sponge films, polyethylene terephthalate It is ester film, polyvinyl butyral film, formaldehyde-phenol film, neoprene film, butadiene-propylene copolymer film, natural One kind in rubber film, polyacrylonitrile film, acrylonitrile vinyl chloride film and polyethylene the third diphenol carbonate thin film.Wherein, The material of the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier can be with identical in principle, it is also possible to no Together.But, if the material of two-layer high molecular polymer insulating barrier is all identical, the quantity of electric charge very little of triboelectrification can be caused.Cause This preferably, the first high molecular polymer insulating barrier is different from the material of the second high molecular polymer insulating barrier.
In addition to above two structure, nano friction generator can also be realized using the third structure, such as Figure 16 a and figure Shown in 16b.Figure 16 a and Figure 16 b respectively illustrate the dimensional structure diagram of the third structure of nano friction generator and cut open Face structural representation.It can be seen that the third structure increased a film between two parties on the basis of second structure Layer, i.e.,：The nano friction generator of the third structure includes the first electrode 161, the first high molecular polymerization that are cascading Thing insulating barrier 162, between two parties film layer 160, the second high molecular polymer insulating barrier 164 and second electrode 163.Specifically, One electrode 161 is arranged on the first side surface of the first high molecular polymer insulating barrier 162；Second electrode 163 is arranged on second On first side surface of high molecular polymer insulating barrier 164, and film layer 160 is arranged on the insulation of the first high molecular polymer between two parties Between 162 the second side surface of layer and the second side surface of the second high molecular polymer insulating barrier 164.Wherein, it is described thin between two parties At least one of two faces that the high molecular polymer insulating barrier 162 of film layer 160 and first is oppositely arranged face is provided with micro-nano knot In structure 165, and/or two faces being oppositely arranged of the high molecular polymer insulating barrier 164 of the film layer between two parties 160 and second extremely A few face is provided with micro-nano structure 165, the specific set-up mode on micro-nano structure 165 can refer to it is described above, herein not Repeat again.
The material of the nano friction generator shown in Figure 16 a and Figure 16 b is referred to the nanometer of second foregoing structure The material of friction generator is selected.Wherein, film layer can also be selected from transparent high polymer poly terephthalic acid second two between two parties Alcohol ester (PET), dimethyl silicone polymer (PDMS), polystyrene (PS), polymethyl methacrylate (PMMA), makrolon (PC) any one and in polymeric liquid crystal copolymer (LCP).Wherein, the first high molecular polymer insulating barrier and second Material preferably clear high polymer polyethylene terephthalate (PET) of high molecular polymer insulating barrier；Wherein, it is described between two parties The preferred dimethyl silicone polymer of the material (PDMS) of film layer.Above-mentioned the first high molecular polymer insulating barrier, the second macromolecule The material of polymer insulation layer, between two parties film layer can be with identical, it is also possible to different.But, if three floor height Molecularly Imprinted Polymers are exhausted The material of edge layer is all identical, can cause the quantity of electric charge very little of triboelectrification, therefore, in order to improve friction effect, film layer between two parties Material be different from the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier, and the first high molecular polymer Insulating barrier is then preferably identical with the material of the second high molecular polymer insulating barrier, so, can reduce material category, makes of the invention Make and more facilitate.
In the implementation shown in Figure 16 a and Figure 16 b, film layer 160 is one layer of polymeric film between two parties, therefore substantially It is similar with the implementation shown in Figure 15 a and Figure 15 b, it is still that (second is high by polymer (film layer between two parties) and polymer Molecularly Imprinted Polymer insulating barrier) between friction generate electricity.Wherein, film layer is easily prepared and stable performance between two parties.
In addition, nano friction generator can also be realized using the 4th kind of structure, and as shown in Figure 17 a and Figure 17 b, bag Include:The first electrode 171 being cascading, the first high molecular polymer insulating barrier 172, intervening electrode layer 170, the second high score Sub- polymer insulation layer 174 and second electrode 173；Wherein, first electrode 171 is arranged on the first high molecular polymer insulating barrier On 172 the first side surface；Second electrode 173 is arranged on the first side surface of the second high molecular polymer insulating barrier 174, is occupied Between electrode layer 170 be arranged on the first high molecular polymer insulating barrier 172 the second side surface and the second high molecular polymer insulation Between second side surface of layer 174.Wherein, the face and residence of the relative intervening electrode layer 170 of the first high molecular polymer insulating barrier 172 Between electrode layer 170 with respect to being provided with micro-nano structure (figure at least one of face face of the first high molecular polymer insulating barrier 172 Do not show)；The face of the relative intervening electrode layer 170 of the second high molecular polymer insulating barrier 174 and intervening electrode layer 170 relative second are high Micro-nano structure (not shown) is provided with least one of the face of Molecularly Imprinted Polymer insulating barrier 174 face.In this fashion, lead to Cross and rubbed between intervening electrode layer 170 and the first high molecular polymer insulating barrier 172 and the second high molecular polymer insulating barrier 174 Electrostatic charge is produced, thus electrical potential difference will be produced between intervening electrode layer 170 and first electrode 171 and second electrode 173, this When, first electrode 171 and the series connection of second electrode 173 are an output electrode of nano friction generator；Intervening electrode layer 170 is Another output electrode of nano friction generator.
In the structure shown in Figure 17 a and Figure 17 b, the first high molecular polymer insulating barrier, the second high molecular polymer are exhausted The material that the material of edge layer, first electrode and second electrode is referred to the nano friction generator of second foregoing structure is entered Row selection.Intervening electrode layer can select conductive film, conducting polymer, metal material, and metal material includes simple metal and conjunction Gold, simple metal is selected from Au Ag Pt Pd, aluminium, nickel, copper, titanium, chromium, selenium, iron, manganese, molybdenum, tungsten, vanadium etc., and alloy can be selected from light conjunction Golden (aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy etc.), weight non-ferrous alloy (copper alloy, kirsite, manganese alloy, nickel alloy etc.), Low-melting alloy (lead, tin, cadmium, bismuth, indium, gallium and its alloy), refractory alloy (tungsten alloy, molybdenum alloy, niobium alloy, tantalum alloy Deng).Preferably 100 μm -500 μm, more preferably 200 μm of the thickness of intervening electrode layer 80.
The self-charging ultracapacitor that the present invention is provided can realize self-charging function, due to being made using flexible material, Allow that whole self-charging ultracapacitor arbitrarily bends, deforms, so that self-charging ultracapacitor of the invention can To adapt to different application application and environment.In addition, the self-charging ultracapacitor that the present invention is provided can realize ultracapacitor Fast charging and discharging, and in discharge process capacitor capability retention it is high, it is possible to achieve more effective discharge and recharge, is one Excellent energy storage device.Except this, the present invention provide self-charging ultracapacitor structure design it is flexible, ingenious, performance more preferably, And shape, size can also be processed according to the demand of user, more facilitation.
Finally it should be noted that be：Listed above is only specific implementation example of the invention, the technology of certain this area Personnel can be modified and modification to the present invention, if these modifications and modification belong to the claims in the present invention and its equivalent skill Within the scope of art, protection scope of the present invention is considered as.

Claims (23)

1. a kind of self-charging ultracapacitor, it is characterised in that including：
At least one nano friction generator of electric energy is converted mechanical energy into, each nano friction generator has for exporting Two output electrodes of electric signal；
Electricity being connected with the output electrode of at least one nano friction generator, exporting the nano friction generator Signal is adjusted the charging circuit module of conversion；And
Electric signal being connected with the charging circuit module, receiving charging circuit module output and stored it is super Capacitor；
Wherein, the charging circuit module includes：Rectification circuit module, filter circuit module, charge control module and switch/change Die block；
The rectification circuit module is connected with the output electrode of at least one nano friction generator, for by described at least one The electric signal of nano friction generator output carries out rectification treatment；
The filter circuit module is connected with the rectification circuit module, for the unidirectional arteries and veins for exporting the rectification circuit module Rush direct current to be filtered treatment and obtain DC signal, the DC signal is exported to the ultracapacitor；
The charge control module is connected with filter circuit module, receives the DC signal of the filter circuit module output； The charge control module is connected with the ultracapacitor, receives the charging voltage of the ultracapacitor feedback；It is described to fill Electric control module is connected with the switch/voltage changing module, and the charge control module is according to the DC signal and described fills Piezoelectric voltage obtains control signal, and the control signal is exported to the switch/voltage changing module；
Switch/the voltage changing module is connected with the filter circuit module, the DC signal of wave reception filtering circuit module output； Switch/the voltage changing module is connected with the ultracapacitor, and the switch/voltage changing module is carried out according to the control signal for receiving Switch switching and the DC signal to filter circuit module output are exported to the super capacitor after carrying out transformation treatment Device；
Wherein, the charge control module is used to be compared the charging voltage U that ultracapacitor feeds back with full of voltage U0, If U is less than U0, show ultracapacitor also underfill, it is necessary to continue to charge；If U is equal to U0, show that ultracapacitor has been filled with； Meanwhile, charge control module is additionally operable to compare the d. c. voltage signal U1 that filter circuit module is exported with U0, if U1 is more than U0, Then charge control module output control signal controlling switch/voltage changing module carries out step-down treatment to U1, obtains ultracapacitor Real time charging voltage U2；If U1 is less than U0, charge control module output control signal controlling switch/voltage changing module is carried out to U1 Boosting is processed, and obtains the real time charging voltage U2 of ultracapacitor.
2. self-charging ultracapacitor according to claim 1, it is characterised in that the ultracapacitor includes：
Substrate；
Barrier film, ultracapacitor first electrode, ultracapacitor second electrode and the first collector, second in substrate Collector, the barrier film is arranged between the ultracapacitor first electrode and ultracapacitor second electrode, and described first Collector is connected with ultracapacitor first electrode, and second collector is connected with ultracapacitor second electrode, described to fill Electric circuit module is connected with first collector, the second collector；
Two bed course pieces on first collector and the second collector are located at respectively；
Formed by described two bed course pieces, the barrier film, the ultracapacitor first electrode and ultracapacitor second electrode Cavity, electrolyte is filled with the cavity；
The encapsulated layer that the electrolyte is packaged.
3. self-charging ultracapacitor according to claim 2, it is characterised in that at least one nano friction generates electricity Machine is arranged on the side of the ultracapacitor, and at least one nano friction generator shares institute with the ultracapacitor State substrate.
4. self-charging ultracapacitor according to claim 2, it is characterised in that at least one nano friction generates electricity Machine sets up separately in the both sides of the ultracapacitor, is arranged at least one nano friction generator on the downside of the ultracapacitor The substrate is shared with the ultracapacitor, at least one nano friction generator on the upside of the ultracapacitor is arranged on Insulating barrier is additionally provided between the ultracapacitor.
5. self-charging ultracapacitor according to claim 1, it is characterised in that the ultracapacitor includes：Successively First collector of parallel stacking, ultracapacitor first electrode, barrier film, ultracapacitor second electrode and the second afflux Body；The charging circuit module is connected with first collector, the second collector.
6. self-charging ultracapacitor according to claim 5, it is characterised in that at least one nano friction generates electricity Machine is arranged on the side of the ultracapacitor, between at least one nano friction generator and the ultracapacitor also It is provided with insulating barrier.
7. self-charging ultracapacitor according to claim 5, it is characterised in that at least one nano friction generates electricity Machine sets up separately in the both sides of the ultracapacitor, is arranged at least one nano friction generator on the downside of the ultracapacitor The first insulating barrier is additionally provided between the ultracapacitor, at least one nanometer on the upside of the ultracapacitor is arranged on The second insulating barrier is additionally provided between friction generator and the ultracapacitor.
8. the self-charging ultracapacitor according to claim 3 or 5, it is characterised in that the nano friction generator has Multiple, and array is arranged in same layer or different layers, forms parallel-connection structure.
9. the self-charging ultracapacitor according to claim 4 or 7, it is characterised in that：
Being arranged on the nano friction generator on the downside of the ultracapacitor has multiple, and array is arranged in same layer or difference Layer, forms parallel-connection structure；
And/or, being arranged on the nano friction generator on the upside of the ultracapacitor has a multiple, and array be arranged in same layer or Different layers, form parallel-connection structure.
10. the self-charging ultracapacitor according to claim 2 or 5, it is characterised in that the ultracapacitor is complete solid State ultracapacitor, selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form activity charcoal super capacitor, complete Solid active charcoal is asymmetric super with metal oxide asymmetric type supercapacitor, all solid state activated carbon and conducting polymer Capacitor, all solid state activated carbon mix the one kind in asymmetric type supercapacitor with lithium ion battery.
11. self-charging ultracapacitors according to claim 2, it is characterised in that the material of the substrate is selected from poly- right One kind in PET, silicon and silica.
12. self-charging ultracapacitors according to claim 2, it is characterised in that the material choosing of described two bed course pieces From buna, butadiene-styrene rubber, nitrile rubber, butyl rubber, silicon rubber, polyurethane rubber, isoprene rubber, butadiene rubber, fluorine One kind in rubber and ACM.
The 13. self-charging ultracapacitor according to claim 2 or 5, it is characterised in that the material of the barrier film is from oxygen Graphite；Polyvinyl alcohol-sulfuric acid system；Polyvinyl alcohol-Phosphoric Acid；1- butyl, 3- methylimidazole bis trifluoromethyl sulfo nyls Acid imide-fumed silica system；Polyaniline -1- ethyls, 3- methyl imidazolium tetrafluoroborates-trimethyl silanol system；1- butyl, 3- methyl imidazolium tetrafluoroborates-silica gel system；Polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate System；Polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid receives system；Polyethylene glycol oxide-polyethylene glycol- Trifluoromethyl sulfonic acid lithium system；Polymethyl methacrylate-ethylene carbonate-propene carbonate-tetraethylammonium perchlorate's system In one kind.
14. self-charging ultracapacitors according to claim 2, it is characterised in that the material of the encapsulated layer is plastic-aluminum Film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, poly-methyl methacrylate One kind in ester, polyformaldehyde, makrolon and PA membrane.
The 15. self-charging ultracapacitor according to claim 2 or 5, it is characterised in that first collector and second The material of collector is selected from the one kind in copper, silver, al and ni；The ultracapacitor first electrode and the electricity of ultracapacitor second The material of pole is selected from Graphene, activated carbon, charcoal-aero gel, carbon fiber, metal oxide, conducting polymer and lithium ion battery battery One kind in the material of pole.
16. self-charging ultracapacitors according to claim 2, it is characterised in that the ultracapacitor first electrode It is with ultracapacitor second electrode：Parallel construction, many column parallel architectures, interdigital structure, serpentine configuration, helical structure, tree Dendritic morphology, spiral dendritic structure or dactylotype.
17. self-charging ultracapacitors according to claim 1, it is characterised in that the charging circuit module also includes： Alternator control modules；
The alternator control modules are connected with the ultracapacitor, receive the charging voltage of the ultracapacitor feedback；
The alternator control modules are connected with the nano friction generator, and the alternator control modules are according to the charging The signal that voltage stops generating electricity to nano friction generator output.
The 18. self-charging ultracapacitor according to any one of claim 1 to 7, it is characterised in that the nano friction hair Motor includes：The first electrode being cascading, the first high molecular polymer insulating barrier, and second electrode；Wherein, it is described First electrode is arranged on the first side surface of the first high molecular polymer insulating barrier；And first high molecular polymer Second side surface of insulating barrier is set towards the second electrode, and the first electrode and second electrode constitute the nano friction The output electrode of generator.
19. self-charging ultracapacitors according to claim 18, it is characterised in that first high molecular polymer is exhausted Edge layer is provided with micro-nano structure towards the face of second electrode.
20. self-charging ultracapacitors according to claim 18, it is characterised in that the nano friction generator enters one Step includes：The second high molecular polymer being arranged between the second electrode and the first high molecular polymer insulating barrier is exhausted Edge layer, the second electrode is arranged on the first side surface of the second high molecular polymer insulating barrier；And it is described second high Second side surface of Molecularly Imprinted Polymer insulating barrier is oppositely arranged with the second side surface of the first high molecular polymer insulating barrier.
21. self-charging ultracapacitors according to claim 20, it is characterised in that first high molecular polymer is exhausted At least one of two faces that edge layer and the second high molecular polymer insulating barrier are oppositely arranged face is provided with micro-nano structure.
22. self-charging ultracapacitors according to claim 20, it is characterised in that the nano friction generator enters one Step includes：It is arranged between the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier between two parties Film layer, wherein, the film layer between two parties is polymer film layer, and the first high molecular polymer insulating barrier is relatively described Between two parties the face of film layer and between two parties film layer relative at least one of the face face of the first high molecular polymer insulating barrier and/ Or the relatively described film layer between two parties of the second high molecular polymer insulating barrier face and between two parties film layer with respect to the second macromolecule At least one of face of polymer insulation layer face is provided with micro-nano structure.
The 23. self-charging ultracapacitor according to any one of claim 1 to 7, it is characterised in that the nano friction hair Motor includes：The first electrode being cascading, the first high molecular polymer insulating barrier, intervening electrode layer, the second macromolecule Polymer insulation layer and second electrode；Wherein, the first electrode is arranged on the first high molecular polymer insulating barrier On first side surface；The second electrode is arranged on the first side surface of the second high molecular polymer insulating barrier, described Intervening electrode layer is arranged on second side surface and second high molecular polymer of the first high molecular polymer insulating barrier Between second side surface of insulating barrier, and the first high molecular polymer insulating barrier intervening electrode layer relatively face and residence Between electrode layer relative at least one of the face face of the first high molecular polymer insulating barrier and/or second polyphosphazene polymer In the face of the relatively described intervening electrode layer of compound insulating barrier and the face of the relative second high molecular polymer insulating barrier of intervening electrode layer At least one face be provided with micro-nano structure, the first electrode and second electrode constitute institute after being connected with intervening electrode layer State the output electrode of nano friction generator.
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