CN104064361A - Self-charging super capacitor - Google Patents

Self-charging super capacitor Download PDF

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Publication number
CN104064361A
CN104064361A CN201310090472.6A CN201310090472A CN104064361A CN 104064361 A CN104064361 A CN 104064361A CN 201310090472 A CN201310090472 A CN 201310090472A CN 104064361 A CN104064361 A CN 104064361A
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CN
China
Prior art keywords
ultracapacitor
electrode
charging
insulating barrier
friction generator
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CN201310090472.6A
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Chinese (zh)
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CN104064361B (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
Publication of CN104064361A publication Critical patent/CN104064361A/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 particularly, relate to a kind of self-charging ultracapacitor.
Background technology
Ultracapacitor, also referred to as electrochemical capacitor, is a kind of electrochemical energy storage device between traditional capacitor and battery.Compare with traditional capacitor, ultracapacitor has higher static capacity; Compare with battery, ultracapacitor has higher power density and overlength cycle life.Ultracapacitor combines the advantage of the two, is a kind of energy storage device having a extensive future.
Existing ultracapacitor is mainly comprised of electrode, electrolyte and barrier film.Wherein electrode comprises electrode active material and collector electrode two parts.The effect of collector electrode is the internal resistance that reduces electrode, requires it and electrode contact area large, and contact resistance is little, and corrosion resistance is strong, at electrolyte performance, stablizes, and chemical reaction etc. does not occur.
Although ultracapacitor superior performance, the source of its charge power supply is single, can not realize self-charging, therefore its use has produced certain limitation.In prior art, also have some ultracapacitors, they can be prepared to flexible structure, but complicated process of preparation is difficult for being produced by large-scale processing.Ultracapacitor is as a kind of desirable energy-storage travelling wave tube in future, and its structure also needs unique design.Therefore,, in order better using and application ultracapacitor, to need badly and address the above problem.
Summary of the invention
Goal of the invention of the present invention is the defect for 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, comprising:
Mechanical energy is converted to at least one nano friction generator of electric energy, each nano friction generator has two output electrodes for output electrical signals;
The charging circuit module being connected with the output electrode of described at least one nano friction generator, the signal of telecommunication of described nano friction generator output is regulated to conversion; And
Be connected with described charging circuit module, the signal of telecommunication that receives the output of described charging circuit module the ultracapacitor storing.
Alternatively, described ultracapacitor comprises:
Substrate;
Be positioned at suprabasil barrier film, ultracapacitor the first electrode, ultracapacitor the second electrode and the first collector, the second collector, described barrier film is arranged between described ultracapacitor the first electrode and ultracapacitor the second electrode, described the first collector is connected with ultracapacitor the first electrode, described the second collector is connected with ultracapacitor the second electrode, and described charging circuit module is connected with described the first collector, the second collector;
Lay respectively at two bed course sheets on described the first collector and the second collector;
The cavity being formed by described two bed course sheets, described barrier film, described ultracapacitor the first electrode and ultracapacitor the second electrode, is filled with electrolyte in described cavity;
The encapsulated layer that described electrolyte is encapsulated.
Alternatively, described at least one nano friction generator is arranged on a side of described ultracapacitor, and described at least one nano friction generator and described ultracapacitor share described substrate.
Alternatively, described at least one nano friction generator divides the both sides that are located at described ultracapacitor, be arranged at least one nano friction generator of described ultracapacitor downside and described ultracapacitor and share described substrate, be arranged between at least one nano friction generator of described ultracapacitor upside and described ultracapacitor and be also provided with insulating barrier.
Alternatively, described ultracapacitor comprises: the first collector of parallel stacked setting, ultracapacitor the first electrode, barrier film, ultracapacitor the second electrode and the second collector and encapsulated layer successively; Described charging circuit module is connected with described the first collector, the second collector.
Alternatively, described at least one nano friction generator is arranged on a side of described ultracapacitor, between described at least one nano friction generator and described ultracapacitor, is also provided with insulating barrier.
Alternatively, described at least one nano friction generator divides the both sides that are located at described ultracapacitor, be arranged between at least one nano friction generator of described ultracapacitor downside and described ultracapacitor and be also provided with the first insulating barrier, be arranged between at least one nano friction generator of described ultracapacitor upside and described ultracapacitor and be also provided with the second insulating barrier.
Alternatively, described nano friction generator has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.
Alternatively, the nano friction generator that is arranged on described ultracapacitor downside has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure; And/or the nano friction generator that is arranged on described ultracapacitor upside has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.
Alternatively, described ultracapacitor is all-solid-state supercapacitor, is selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.
Alternatively, the material of described substrate is selected from a kind of in PETG, silicon and silicon dioxide.
Alternatively, the material of described two bed course sheets is selected from a kind of in buna, butadiene-styrene rubber, acrylonitrile-butadiene rubber, butyl rubber, silicon rubber, polyurethane rubber, isoprene rubber, butadiene rubber, fluorubber and acrylate rubber.
Alternatively, the material of described barrier film is autoxidation graphite; Polyvinyl alcohol-sulfuric acid system; Polyvinyl alcohol-Phosphoric Acid; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; Polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; Polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate system; Polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received system; Polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium system; A kind of in polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium system.
Alternatively, the material of described encapsulated layer is a kind of in aluminum plastic film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polyformaldehyde, Merlon and polyamide membrane.
Alternatively, the material of described the first collector and the second collector is selected from a kind of in copper, silver, al and ni; The material of described ultracapacitor the first electrode and ultracapacitor the second electrode is selected from a kind of in Graphene, active carbon, charcoal-aero gel, carbon fiber, metal oxide, conducting polymer and lithium ion battery electrode material.
Alternatively, described ultracapacitor the first electrode and ultracapacitor the second electrode are: parallel construction, multiple row parallel construction, interdigital structure, serpentine configuration, helical structure, dendritic structure, spiral dendritic structure or dactylotype.
Alternatively, described charging circuit module comprises:
The rectification circuit module being connected with the output electrode of at least one nano friction generator, the signal of telecommunication of described at least one nano friction generator output is carried out to rectification processing; And
Be connected with described rectification circuit module, the unidirectional pulse direct current of described rectification circuit module output carried out to filtering processing and obtain the filter circuit module of DC signal, described filter circuit module is exported to described ultracapacitor by described DC signal.
Alternatively, described charging circuit module also comprises: charge control module and switch/voltage changing module;
Described charge control module is connected with filter circuit module, receives the DC signal of described filter circuit module output; Described charge control module is connected with described ultracapacitor, receives the charging voltage of described ultracapacitor feedback; Described charge control module is connected with described switch/voltage changing module, and described charge control module, according to described DC signal and the controlled signal of described charging voltage, is exported described control signal to described switch/voltage changing module;
Described switch/voltage changing module is connected with described filter circuit module, the DC signal of wave reception filtering circuit module output; Described switch/voltage changing module is connected with described ultracapacitor, and described switch/voltage changing module carries out switching over according to the control signal receiving and the DC signal of described filter circuit module output is carried out exporting to described ultracapacitor after transformation processing.
Alternatively, described charging circuit module also comprises: generator control module; Described generator control module is connected with described ultracapacitor, receives the charging voltage of described ultracapacitor feedback; Described generator control module is connected with described nano friction generator, and described generator control module stops the signal of generating to described nano friction generator output according to described charging voltage.
Alternatively, described nano friction generator comprises: the first electrode being cascading, the first high molecular polymer insulating barrier, and the second electrode; Wherein, described the first electrode is arranged on the first side surface of described the first high molecular polymer insulating barrier; And the second side surface of described the first high molecular polymer insulating barrier is towards described the second electrode setting, and described the first electrode and the second electrode form the output electrode of described nano friction generator.
Alternatively, described the first high molecular polymer insulating barrier is provided with micro-nano structure towards the face of the second electrode.
Alternatively, described nano friction generator further comprises: be arranged on the second high molecular polymer insulating barrier between described the second electrode and described the first high molecular polymer insulating barrier, described the second electrode is arranged on the first side surface of described the second high molecular polymer insulating barrier; And the second side surface of the second side surface of described the second high molecular polymer insulating barrier and described the first high molecular polymer insulating barrier is oppositely arranged.
Alternatively, at least one face in two faces that described the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier are oppositely arranged is provided with micro-nano structure.
Alternatively, described nano friction generator further comprises: be arranged on the thin layer between two parties between described the first high molecular polymer insulating barrier and described the second high molecular polymer insulating barrier, wherein, described thin layer is between two parties polymer film layer, and described the first high molecular polymer insulating barrier relatively described between two parties thin layer face and thin layer between two parties with respect at least one face in the face of the first high molecular polymer insulating barrier and/or described the second high molecular polymer insulating barrier relative described between two parties at least one face in the face of thin layer and the face of relative the second high molecular polymer insulating barrier of thin layer be between two parties provided with micro-nano structure.
Alternatively, described nano friction generator comprises: the first electrode being cascading, the first high molecular polymer insulating barrier, electrode layer between two parties, the second high molecular polymer insulating barrier and the second electrode, wherein, described the first electrode is arranged on the first side surface of described the first high molecular polymer insulating barrier, described the second electrode is arranged on the first side surface of described the second high molecular polymer insulating barrier, described electrode layer is between two parties arranged between the second side surface of described the first high molecular polymer insulating barrier and the second side surface of described the second high molecular polymer insulating barrier, and described the first high molecular polymer insulating barrier relatively described between two parties electrode layer face and electrode layer between two parties with respect at least one face in the face of the first high molecular polymer insulating barrier and/or described the second high molecular polymer insulating barrier relative described between two parties at least one face in the face of electrode layer and the face of relative the second high molecular polymer insulating barrier of electrode layer be between two parties provided with micro-nano structure, after being connected with the second electrode, described the first electrode forms the output electrode of described nano friction generator with described electrode layer between two parties.
In self-charging ultracapacitor provided by the invention, nano friction generator has served as the role of charge power supply, it is by being converted to electric energy by mechanical energy, after electric power signal being regulated to conversion by charging circuit module again, export to ultracapacitor and store, thereby realized the self-charging of ultracapacitor.
Accompanying drawing explanation
Fig. 1 is the theory structure block diagram of self-charging ultracapacitor provided by the invention;
Fig. 2 is the perspective view of the embodiment mono-of self-charging ultracapacitor provided by the invention;
Fig. 3 is the schematic cross-section of the embodiment mono-of self-charging ultracapacitor provided by the invention;
Fig. 4 a-Fig. 4 h is the schematic top plan view of the structure between ultracapacitor the first electrode and ultracapacitor the second electrode;
Fig. 5 is a kind of circuit theory schematic diagram of the embodiment mono-of self-charging ultracapacitor provided by the invention;
Fig. 6 is the another kind of circuit theory schematic diagram of the embodiment mono-of self-charging ultracapacitor provided by the invention;
Fig. 7 shows the schematic diagram that is set up in parallel a plurality of nano friction generators with layer;
Fig. 8 is the perspective view of the embodiment bis-of self-charging ultracapacitor provided by the invention;
Fig. 9 is the schematic cross-section of the embodiment bis-of self-charging ultracapacitor provided by the invention;
Figure 10 is the perspective view of the embodiment tri-of self-charging ultracapacitor provided by the invention;
Figure 11 is the schematic cross-section of the embodiment tri-of self-charging ultracapacitor provided by the invention;
Figure 12 is the perspective view of the embodiment tetra-of self-charging ultracapacitor provided by the invention;
Figure 13 is the schematic cross-section of the embodiment tetra-of self-charging ultracapacitor provided by the invention;
Figure 14 a and Figure 14 b show respectively perspective view and the cross-sectional view of the first structure of nano friction generator;
Figure 15 a and Figure 15 b show respectively perspective view and the cross-sectional view of the second structure of nano friction generator;
Figure 16 a and Figure 16 b show respectively perspective view and the cross-sectional view of the third structure of nano friction generator;
Figure 17 a and Figure 17 b show respectively perspective view and the cross-sectional view of the 4th kind of structure of nano friction generator.
Embodiment
For fully understanding the present invention's object, feature and effect, by following concrete execution mode, the present invention is elaborated, but the present invention is not restricted to this.
Fig. 1 is the theory structure block diagram of self-charging ultracapacitor provided by the invention.As shown in Figure 1, this self-charging ultracapacitor comprises nano friction generator 11, charging circuit module 12 and ultracapacitor 13.Fig. 1 is only a schematic diagram, and in practice, self-charging ultracapacitor can comprise one or more nano friction generators, and each nano friction generator has two output electrodes for output electrical signals.The output electrode of nano friction generator 11 is connected with charging circuit module 12, and charging circuit module 12 is connected with ultracapacitor 13.The basic functional principle of this self-charging ultracapacitor is: under the effect of external force, mechanical deformation occurs nano friction generator 11, and mechanical energy is converted to electric energy; Afterwards, the output electrode of nano friction generator 11 is exported to charging circuit module 12 by the signal of telecommunication; Charging circuit module 12 is exported to ultracapacitor 13 after this signal of telecommunication is regulated to conversion, and ultracapacitor 13 receives the signal of telecommunication after this adjusting conversion and stores, and in order to external electric equipment, uses.
In the self-charging ultracapacitor providing at the present embodiment, nano friction generator has served as the role of charge power supply, it is by being converted to electric energy by mechanical energy, after electric power signal being regulated to conversion by charging circuit module again, export to ultracapacitor and store, thereby realized the self-charging of ultracapacitor.
Fig. 2 is the perspective view of the embodiment mono-of self-charging ultracapacitor provided by the invention.As shown in Figure 2, this self-charging ultracapacitor comprises: ultracapacitor 21 and a nano friction generator 22 that is arranged on a side of ultracapacitor 21.Wherein, nano friction generator 22 is placed in bottom, and ultracapacitor 21 is arranged on the upper surface of nano friction generator 22, and nano friction generator 22 forms an integral body with ultracapacitor 21.Not shown charging circuit module in Fig. 2.Two output electrodes of nano friction generator 22 are connected with charging circuit module, and charging circuit module is connected with ultracapacitor 21 again, thereby realize the storage of electric energy.
In the present embodiment, ultracapacitor 21 is all-solid-state supercapacitor, is selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.Preferably, ultracapacitor 21 is selected from all solid state symmetric form Graphene ultracapacitor.
Fig. 3 is the schematic cross-section of the embodiment mono-of self-charging ultracapacitor provided by the invention.In conjunction with Fig. 3, take the structure of all solid state symmetric form Graphene ultracapacitor as example explanation ultracapacitor.As shown in Figure 3, ultracapacitor comprises: substrate 31, be positioned at barrier film 32, ultracapacitor the first electrode 33, ultracapacitor the second electrode 34 and the first collector 35, the second collector 36 in substrate 31, two bed course sheets 37, be filled with the cavity 38 of electrolyte, the encapsulated layer 39 that electrolyte is encapsulated.Its septation 32 is graphite oxide, and ultracapacitor the first electrode 33 and ultracapacitor the second electrode 34 are Graphene, and the first collector 35 and the second collector 36 are metal tape.Barrier film 32 is arranged between ultracapacitor the first electrode 33 and ultracapacitor the second electrode 34, and in Fig. 3, ultracapacitor the first electrode 33 and ultracapacitor the second electrode 34 are positioned at barrier film 32 both sides; The first collector 35 is connected with ultracapacitor the first electrode 33 by conducting resinl, the second collector 36 is connected with ultracapacitor the second electrode 34 by conducting resinl, in Fig. 3, the first collector 35 is positioned at the outside of ultracapacitor the first electrode 33, and the second collector 36 is positioned at the outside of ultracapacitor the second electrode 34.On two collectors, be provided with two bed course sheets 37, by these two bed course sheets 37, barrier film 32, ultracapacitor the first electrode 33 and ultracapacitor the second electrode 34, be formed with cavity 38, for filling electrolyte.Encapsulated layer 39 encapsulates electrolyte, thereby forms very thin ultracapacitor.
Nano friction generator in Fig. 3 is layer structure, comprising: friction electrode 30A, high molecular polymer insulating barrier 30B and electrode 30C.Wherein nano friction generator and ultracapacitor common base 31.The structure of this nano friction generator will describe in detail in the back.
In the present embodiment, the material of substrate 31 is selected from PETG (PET), silicon (Si) and silicon dioxide (SiO 2) in a kind of.
The material of the first collector 35 and the second collector 36 is selected from a kind of in copper, silver, al and ni, particularly, can be copper or silver etc. in PVA system during as electrolyte, can be aluminium or nickel etc. in ionic liquid system during as electrolyte.
The material of ultracapacitor the first electrode 33 and ultracapacitor the second electrode 34 is selected from a kind of in Graphene, active carbon, charcoal-aero gel, 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-H 2sO 4(polyvinyl alcohol-sulfuric acid) system; PVA-H 3pO 4(polyvinyl alcohol-phosphoric acid) system; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; PAN-[EMIm] BF 4-TMS(polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol) system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; PMMA-EC-PC-LiClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate) system; PMMA-EC-PC-NaClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received) system; PEO-PEG-LiCF 3sO 3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system; PMMA-EC-PC-TEAClO 4a kind of in (polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium) system.
The material of two bed course sheets 37 is selected from a kind of in buna, butadiene-styrene rubber, acrylonitrile-butadiene rubber, butyl rubber, silicon rubber, polyurethane rubber, isoprene rubber, butadiene rubber, fluorubber and acrylate rubber.
Electrolyte is solid-state or colloidal state, and the system of electrolyte is PVA-H 2sO 4(polyvinyl alcohol-sulfuric acid) system; PVA-H 3pO 4(polyvinyl alcohol-phosphoric acid) system; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; PAN-[EMIm] BF 4-TMS(polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol) system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; PMMA-EC-PC-LiClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate) system; PMMA-EC-PC-NaClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received) system; PEO-PEG-LiCF 3sO 3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system; PMMA-EC-PC-TEAClO 4a kind of in (polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium) system.
The material of encapsulated layer 39 is a kind of in aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyformaldehyde (POM), Merlon (PC) and polyamide (PA).
In the present embodiment, the structure between ultracapacitor the first electrode and ultracapacitor the second electrode can have multiple, and Fig. 4 a-Fig. 4 h is the schematic top plan view of the structure between ultracapacitor the first electrode and ultracapacitor the second electrode.Shown in Fig. 4 a is parallel construction, and ultracapacitor the first electrode 41A is parallel with ultracapacitor the second electrode 41B, is provided with barrier film 41C between the two.Shown in Fig. 4 b is multiple row parallel construction, and wherein electrode 42A has multiple row and parallel to each other.Shown in Fig. 4 c is interdigital structure, between ultracapacitor the first electrode 43A and ultracapacitor the second electrode 43B, is provided with barrier film 43C, and shown in Fig. 3 is exactly such interdigital structure.Shown in Fig. 4 d is serpentine configuration, between ultracapacitor the first electrode 44A and ultracapacitor the second electrode 44B, is barrier film.Shown in Fig. 4 e is helical structure, between ultracapacitor the first electrode 45A and ultracapacitor the second electrode 45B, is barrier film.Shown in Fig. 4 f is dendritic structure, between ultracapacitor the first electrode 46A and ultracapacitor the second electrode 46B, is barrier film.Shown in Fig. 4 g is spiral dendritic structure, between ultracapacitor the first electrode 47A and ultracapacitor the second electrode 47B, is barrier film.Shown in Fig. 4 h is dactylotype, between ultracapacitor the first electrode 48A and ultracapacitor the second electrode 48B, is barrier film.
Above-mentioned all solid state symmetric form Graphene ultracapacitor preferably adopts laser method preparation, and its step comprises:
(1) substrate (as PET) is adhered on CD;
(2) the graphite oxide aqueous solution (1-10mg/ml, the Hummers method of the manufacture method of graphite oxide for improving) is dripped and is coated onto in PET substrate, dry moisture and leave golden brown graphite oxide;
(3) above-mentioned CD is put in dvd CD writer, carried out structure fabrication, generate black graphene-structured;
(4) in graphene-structured both sides, with conductive silver glue, paste copper strips collector;
(5) on the basis of step (4), place the three-back-shaped bed course sheet of sealing use;
(6) in three-back-shaped bed course sheet, splash into gluey electrolyte transpiring moisture;
(7) overall package obtains flexible solid electrolyte ultracapacitor.
Owing to acting on the uncertainty of the external force size of nano friction generator, the alternating current size that nano friction generator is produced is also uncertain, such as: single nano friction generator is under external force is patted, can export the voltage of supreme kilovolt of several volts, this particularity just requires the appropriate design of external circuit to make it reach stable output.The present invention regulates conversion to realize stable output by charging circuit module to the signal of telecommunication of nano friction generator output.
Fig. 5 is a kind of circuit theory schematic diagram of the embodiment mono-of self-charging ultracapacitor provided by the invention.The internal structure that Fig. 5 shows charging circuit module with and with the annexation of nano friction generator and ultracapacitor.As shown in Figure 5, charging circuit module comprises: rectification circuit module 51 and filter circuit module 52.Wherein, rectification circuit module 51 is connected with the output electrode of at least one nano friction generator, and the signal of telecommunication of at least one nano friction generator output is carried out to rectification processing.Particularly, two input 51A of rectification circuit module 51 and 51B are connected respectively two output electrodes of nano friction generator 53, receive the signal of telecommunication of nano friction generator 53 outputs.For the structure that comprises a plurality of nano friction generators, two output electrodes of a plurality of nano friction generators are connected in parallel, and are then connected with 51B with two input 51A of rectification circuit module 51.
Two output 51C of rectification circuit module 51 are connected with filter circuit module 52 with 51D, and the unidirectional pulse direct current that rectification circuit module 51 carries out the signal of telecommunication of nano friction generator 53 outputs to obtain after rectification processing is exported to filter circuit module 52.Filter circuit module 52 is connected with ultracapacitor 54, and filter circuit module 52 carries out filtering processing by the unidirectional pulse direct current of rectification circuit module 51 output and obtains DC signal and export to ultracapacitor 54.
As shown in Figure 5, filter circuit module 52 has two ends.Particularly, the first end 52A of filter circuit module 52 is connected with the output 51D of rectification circuit module 51, and the second end 52B of filter circuit module 52 is connected with the output 51C of rectification circuit module 51.The first end 52A of filter circuit module 52 is connected with the first collector of ultracapacitor, and the second end 52B of filter circuit module 52 is connected with the second collector of ultracapacitor.In actual applications, the general ground connection of the second end 52B of filter circuit module 52.
For the circuit shown in Fig. 5, when External Force Acting is during in nano friction generator, can make nano friction generator generation mechanical deformation, thereby produce the pulse electrical signal exchanging.First the pulse electrical signal of this interchange inputs to rectification circuit module, by rectification circuit module, it is carried out to rectification, obtains the direct current of unidirectional pulsation.The direct current of this unidirectional pulsation inputs to again filter circuit module and carries out filtering, and the interference noise in the direct current of unidirectional pulsation is carried out to filtering, obtains DC signal.Finally, this DC signal directly inputs to ultracapacitor and charges.Here can, for a ultracapacitor charging, also can charge for the ultracapacitor of a plurality of parallel connections simultaneously.
The advantage of foregoing circuit is: (1) produces the size of electric energy and the size of ultracapacitor electric capacity and charging voltage according to nano friction generator, by regulating the relevant parameter of filter circuit module, make it possible to the electric energy that utilizes to greatest extent nano friction generator to produce, improve energy conversion efficiency; (2) according to the difference of applied environment, the voltage amplitude scope that nano friction generator produces is larger, can be adjusted into the voltage adapting to ultracapacitor charging by regulating the relevant parameter of filter circuit module, be overcome the uncertainty that nano friction generator produces voltage swing.
Further, charging circuit module can also adopt a kind of more preferred structure.Fig. 6 is the another kind of circuit theory schematic diagram of the embodiment mono-of self-charging ultracapacitor provided by the invention.The internal structure that Fig. 6 shows preferred charging circuit module with and with the annexation of nano friction generator and ultracapacitor.As shown in Figure 6, charging circuit module, except comprising rectification circuit module 61 and filter circuit module 62, also comprises charge control module 63 and switch/voltage changing module 64.Wherein the function of rectification circuit module 61 and filter circuit module 62, referring to above, repeats no more.
Charge control module 63 is connected with filter circuit module 62, the d. c. voltage signal U1 of wave reception filtering circuit module 62 outputs; Charge control module 63 is connected with ultracapacitor 65, receives the charging voltage U of ultracapacitor 65 feedbacks, and this charging voltage U is the voltage signal forming between two collectors of ultracapacitor 65; Charge control module 63 is also connected with switch/voltage changing module 64, and charge control module 63 is according to d. c. voltage signal U1 and the controlled signal of charging voltage U, to switch/voltage changing module 64 output control signals.Switch/voltage changing module 64 is connected with filter circuit module 62, the d. c. voltage signal U1 of wave reception filtering circuit module 62 outputs; Switch/voltage changing module 64 is also connected with ultracapacitor 65, switch/voltage changing module 64 carries out switching over and the d. c. voltage signal of filter circuit module 62 outputs is regulated to processing according to the control signal receiving, and is adjusted to the voltage U 2 adapting to ultracapacitor 65 chargings.
For the circuit shown in Fig. 6, different from Fig. 5, to process after filtering the d. c. voltage signal U1 obtaining and input to charge control module 63, charge control module 63 can, according to the size of this d. c. voltage signal U1, decide and when ultracapacitor 65 be charged; And ultracapacitor 65 charge conditions are paid close attention to, according to the situation of ultracapacitor 65 chargings, carried out control switch/voltage changing module 64.The output voltage of circuit module 62 is output voltages that progressively increase after filtering, and this output voltage is until increase to pressure limiting voltage, and this pressure limiting voltage is a circuit protection voltage, prevents circuit because overtension and damages.
Because whole charging circuit module does not have external power supply, it is also to come from nano friction generator electricity that charge control module 63 control switchs/voltage changing module 64 is given the working power of ultracapacitor 65 chargings, therefore specially in charge control module 63, a starting resistor is set, after filter circuit module 62 output voltages reach this starting resistor, charge control module 63 just driving switch/voltage changing module 64 starts charging.
Another effect of charge control module 63 is according to the size of d. c. voltage signal U1 and the size of ultracapacitor 65 charging voltage U that obtain after filtering, to d. c. voltage signal, U1 regulates, be adjusted to the voltage U 2 that adapts to ultracapacitor 65 chargings, and selectivity driving switch/voltage changing module 64 gives ultracapacitor 65 chargings.
Known according to C=Q/U, the capacity C of ultracapacitor is a fixed value, and in the process to ultracapacitor charging, quantity of electric charge Q is in continuous increase, and the voltage U of ultracapacitor is also in continuous rising thereupon.For more effective, to ultracapacitor, charge, charge control module 63 is according to the numerical information of the d. c. voltage signal U1 of the charging voltage U of ultracapacitor 65 feedbacks and filter circuit module 62 outputs, carry out the circuit in by-pass cock/voltage changing module 64, realization is the conversion to U2 to voltage U 1, obtains the real time charging voltage U 2 of ultracapacitor 65.Between U2 and U, there is a corresponding charging matching relationship, to guarantee the highest energy conversion efficiency.For instance, suppose that the voltage that is full of of ultracapacitor 65 is U0, charge control module 63 compares charging voltage U and the U0 of ultracapacitor 65 feedbacks, if U is less than U0, shows ultracapacitor 65 also underfills, needs to continue charging; If U equals U0, show that ultracapacitor 65 has been full of.Simultaneously, charge control module 63 is also by d. c. voltage signal U1 and the U0 comparison of filter circuit module 62 outputs, if U1 is greater than U0,64 couples of U1 of charge control module 63 output control signal control switch/voltage changing modules carry out step-down processing, obtain the real time charging voltage U 2 of ultracapacitor 65; If U1 is less than U0,64 couples of U1 of charge control module 63 output control signal control switch/voltage changing modules processing of boosting, obtains the real time charging voltage U 2 of ultracapacitor 65.
Here can be a ultracapacitor charging, also can as Fig. 6, show three ultracapacitors for a plurality of ultracapacitor chargings, these three ultracapacitors be connected in parallel.When being a plurality of ultracapacitor charging, can be full of one by one, also can be full of simultaneously.Be full of and be achieved in the following ways one by one: charge control module 63 is full of voltage U 0 by the charging voltage U of current ultracapacitor feedback of charging and compares with it, if U has reached U0, charge control module 63 output control signal control switch/voltage changing modules 64, by switching over to next ultracapacitor, continue as next ultracapacitor and charge so.
Further, in order to protect nano friction generator, charging circuit module can also comprise generator control module 66.This generator control module 66 is connected with ultracapacitor 65, receives the charging voltage U of ultracapacitor 65 feedbacks, and this charging voltage U is the voltage signal forming between two collectors of ultracapacitor 65; Generator control module 66 is also connected with nano friction generator, stops the signal of generating to the output of nano friction generator.When ultracapacitor 65 is full of, can obtain one and be full of voltage, this is full of Voltage Feedback to generator control module 66, and then generator control module 66 can close nano friction generator, thereby stops generating.
The advantage of the circuit shown in Fig. 6 is: (1) is owing to acting on external force size uncertain of nano friction generator, the alternating current size that nano friction generator is produced is also uncertain, this circuit can convert uncertain magnitude of voltage to the magnitude of voltage that is applicable to ultracapacitor charging, strong adaptability, has expanded the application of self-charging ultracapacitor; (2) due to special design in circuit charge control module, according to the real-time voltage of ultracapacitor, regulate its charging voltage, make real-time voltage and the charging voltage of ultracapacitor keep a Dynamic Matching relation, reached the electric energy that nano friction generator sends is filled to greatest extent to ultracapacitor, realized maximum energy storage effect; (3) according to being full of of ultracapacitor, whether the work of generator control module controls nano friction generator, and then extend the useful life of nano friction generator; (4) when charging for a plurality of ultracapacitors, when one of them is full of, can automatically switches to next ultracapacitor and charge.
The self-charging ultracapacitor that the present embodiment provides is not limited only to comprise single nano friction generator, in a side of ultracapacitor, a plurality of nano friction generators can also be set.Specifically, the nano friction generator that is arranged on ultracapacitor one side has a plurality of, and these nano friction generator arrayed are at same layer or different layers, and the output electrode of their correspondences is joined together to form parallel-connection structure.Its arrangement can be with reference to Fig. 7.The voltage producing with single nano friction generator feature large, that electric current is less is compared, and a plurality of nano friction generators of parallel connection can increase the output of electric current, reach better charging effect; And because a plurality of nano friction generators are evenly distributed, can make it stressed evenly, there is good linear superposition effect.
Fig. 8 is the perspective view of the embodiment bis-of self-charging ultracapacitor provided by the invention.As shown in Figure 8, this self-charging ultracapacitor comprises: ultracapacitor 81 and minute be located at the nano friction generator 82 and 83 of ultracapacitor 81 both sides, similar " sandwich " structure.Wherein, nano friction generator 82 is arranged on the downside of ultracapacitor 81, and nano friction generator 83 is arranged on the upside of ultracapacitor 81.Ultracapacitor 81 forms an integral body with the nano friction generator 82 and 83 of upper and lower both sides.Not shown charging circuit module in Fig. 8.Nano friction generator 82 is connected in parallel and is connected with charging circuit module with 83 two output electrodes separately, and charging circuit module is connected with two collectors of ultracapacitor 81 again, thereby realizes the storage of electric energy.
In the present embodiment, ultracapacitor 81 is all-solid-state supercapacitor, is selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.Preferably, ultracapacitor 81 is selected from all solid state symmetric form Graphene ultracapacitor.
Fig. 9 is the schematic cross-section of the embodiment bis-of self-charging ultracapacitor provided by the invention.As shown in Figure 9, the structure of ultracapacitor 81 is described identical with embodiment mono-, and the available material of its device comprising is also described identical with embodiment mono-, does not repeat them here.Nano friction generator 82 and 83 is layer structure, will describe in detail in the back.Nano friction generator 82 and ultracapacitor 81 common base, be also provided with insulating barrier 90 between nano friction generator 83 and ultracapacitor 81.It should be noted that herein, when nano friction generator and ultracapacitor common base, need not add insulating barrier, when nano friction generator and ultracapacitor do not have common base, need to add insulating barrier, prevent conducting.
In the present embodiment, yet identical with described in embodiment mono-of charging circuit module, does not repeat them here.
The self-charging ultracapacitor that the present embodiment provides is not limited only to comprise upper and lower two nano friction generators, upside and/or downside at ultracapacitor can arrange a plurality of nano friction generators, specifically, specifically, the nano friction generator that is arranged on ultracapacitor downside can have a plurality of, and arrayed, at same layer or different layers, forms parallel-connection structure; And/or the nano friction generator that is arranged on ultracapacitor upside can have a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.Its arrangement can be with reference to Fig. 7.A plurality of nano friction generators of parallel connection can increase the output of electric current, reach better charging effect; And because a plurality of nano friction generators are evenly distributed, can make it stressed evenly, there is good linear superposition effect.
Figure 10 is the perspective view of the embodiment tri-of self-charging ultracapacitor provided by the invention.As shown in figure 10, this self-charging ultracapacitor comprises: ultracapacitor 101 and a nano friction generator 102 that is arranged on ultracapacitor 101 1 sides, be also provided with insulating barrier 103 between nano friction generator 102 and ultracapacitor 101.Wherein, nano friction generator 102 is placed in bottom, and insulating barrier 103 is positioned at the upper surface of nano friction generator 102, and ultracapacitor 101 is positioned at the upper surface of insulating barrier 103.Ultracapacitor 101, insulating barrier 103 and nano friction generator 102 form an integral body.Not shown charging circuit module in Figure 10.Two output electrodes of nano friction generator 102 are connected with charging circuit module, and charging circuit module is connected with two collectors of ultracapacitor 101 again, thereby realize the storage of electric energy.
In the present embodiment, ultracapacitor 101 is all-solid-state supercapacitor, is selected from complete solid symmetrical kenel Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.Preferably, ultracapacitor 101 is selected from all solid state symmetric form Graphene ultracapacitor.
Figure 11 is the schematic cross-section of the embodiment tri-of self-charging ultracapacitor provided by the invention.As shown in figure 11, ultracapacitor comprises: the first collector 111 of parallel stacked setting, ultracapacitor the first electrode 112, barrier film 113, ultracapacitor the second electrode 114 and the second collector 115 successively, ultracapacitor also comprises encapsulated layer (not shown in Figure 11) in addition.Insulating barrier 103 is connected with the first collector 111 contacts.Nano friction generator 102 in Figure 11 is layer structure, and its concrete structure will describe in detail in the back.
In the present embodiment, the material of the first collector 111 and the second collector 115 is selected from a kind of in copper, silver, al and ni.
The material of ultracapacitor the first electrode 112 and ultracapacitor the second electrode 114 is selected from a kind of in Graphene, active carbon, 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-H 2sO 4(polyvinyl alcohol-sulfuric acid) system; PVA-H 3pO 4(polyvinyl alcohol-phosphoric acid) system; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; PAN-[EMIm] BF 4-TMS(polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol) system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; PMMA-EC-PC-LiClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate) system; PMMA-EC-PC-NaClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received) system; PEO-PEG-LiCF 3sO 3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system; PMMA-EC-PC-TEAClO 4a kind of in (polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium) system.
Electrolyte is solid-state or colloidal state, and the system of electrolyte is PVA-H 2sO 4(polyvinyl alcohol-sulfuric acid) system; PVA-H 3pO 4(polyvinyl alcohol-phosphoric acid) system; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; PAN-[EMIm] BF 4-TMS(polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol) system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; PMMA-EC-PC-LiClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate) system; PMMA-EC-PC-NaClO 4(polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received) system; PEO-PEG-LiCF 3sO 3(polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium) system; PMMA-EC-PC-TEAClO 4a kind of in (polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium) system.
The material of encapsulated layer is a kind of in aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), polymethyl methacrylate (PMMA), polyformaldehyde (POM), Merlon (PC) and polyamide (PA).
In the present embodiment, yet identical with described in embodiment mono-of charging circuit module, does not repeat them here.Charging circuit module is connected with the second collector 115 with above-mentioned the first collector 111.
The self-charging ultracapacitor that the present embodiment provides is not limited only to comprise single nano friction generator, a side at ultracapacitor can also arrange a plurality of nano friction generators specifically, the nano friction generator that is arranged on ultracapacitor one side has a plurality of, these nano friction generator arrayed are at same layer or different layers, and the output electrode of their correspondences is joined together to form parallel-connection structure.Its arrangement can be with reference to Fig. 7.The voltage producing with single nano friction generator feature large, that electric current is less is compared, and a plurality of nano friction generators of parallel connection can increase the output of electric current, reach better charging effect; And because a plurality of nano friction generators are evenly distributed, can make it stressed evenly, there is good linear superposition effect.
Figure 12 is the perspective view of the embodiment tetra-of self-charging ultracapacitor provided by the invention.As shown in figure 12, this self-charging ultracapacitor comprises: ultracapacitor 121 and minute be located at the nano friction generator 122 and 123 of ultracapacitor 121 both sides.Wherein, nano friction generator 122 is arranged on the downside of ultracapacitor 121, is also provided with the first insulating barrier 124 between nano friction generator 122 and ultracapacitor 121; Nano friction generator 123 is arranged on the upside of ultracapacitor 121, is also provided with the second insulating barrier 125 between nano friction generator 123 and ultracapacitor 121.The nano friction generator 122,123 of ultracapacitor 121 and upper and lower both sides and the first insulating barrier 124, the second insulating barrier 125 form an integral body.Not shown charging circuit module in Figure 12.Nano friction generator 122 is connected in parallel and is connected with charging circuit module with 123 two output electrodes separately, and charging circuit module is connected with two collectors of ultracapacitor 121 again, thereby realizes the storage of electric energy.
In the present embodiment, ultracapacitor 121 is all-solid-state supercapacitor, is selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.Preferably, ultracapacitor 121 is selected from all solid state symmetric form Graphene ultracapacitor.
Figure 13 is the schematic cross-section of the embodiment tetra-of self-charging ultracapacitor provided by the invention.As shown in figure 13, the structure of ultracapacitor 121 is described identical with embodiment tri-, and the available material of its device comprising is also described identical with embodiment tri-, does not repeat them here.Nano friction generator 122 and 123 is layer structure, will describe in detail in the back.Between nano friction generator 122 and ultracapacitor 121, be provided with the first insulating barrier 124, between nano friction generator 123 and ultracapacitor 121, be provided with the second insulating barrier 125.
In the present embodiment, yet identical with described in embodiment mono-of charging circuit module, does not repeat them here.
The self-charging ultracapacitor that the present embodiment provides is not limited only to comprise upper and lower two nano friction generators, upside and/or downside at ultracapacitor can arrange a plurality of nano friction generators, specifically, the nano friction generator that is arranged on ultracapacitor downside can have a plurality of, and arrayed, at same layer or different layers, forms parallel-connection structure; And/or the nano friction generator that is arranged on ultracapacitor upside can have a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.Its arrangement can be with reference to Fig. 7.A plurality of nano friction generators of parallel connection can increase the output of electric current, reach better charging effect; And because a plurality of nano friction generators are evenly distributed, can make it stressed evenly, there is good linear superposition effect.
Structure and the operation principle of the nano friction generator in self-charging ultracapacitor will be introduced 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 show respectively perspective view and the cross-sectional view of the first structure of nano friction generator.This nano friction generator comprises: the first electrode 141, the first high molecular polymer insulating barriers 142 that are cascading, and the second electrode 143.Particularly, the first electrode 141 is arranged on the first side surface of the first high molecular polymer insulating barrier 142; And the Surface Contact friction of the second side surface of the first high molecular polymer insulating barrier 142 and the second electrode 143 also induces electric charge at the second electrode and the first electrode place.Therefore, the first above-mentioned electrode 141 and the second electrode 143 form two output electrodes of nano friction generator.
In order to improve the generating capacity of nano friction generator, at second side surface (being on the face of relative the second electrode 143) of the first high molecular polymer insulating barrier 142, be further provided with micro-nano structure 144.Therefore, when nano friction generator is squeezed, apparent surface's contact friction better of the first high molecular polymer insulating barrier 142 and the second electrode 143, and induce more electric charge at the first electrode 141 and the second electrode 143 places.Because the second above-mentioned electrode 143 is mainly used in and the first high molecular polymer insulating barrier 142 frictions, therefore, the second electrode 143 also can be referred to as the electrode that rubs.
Above-mentioned micro-nano structure 144 specifically can be taked following two kinds of possible implementations: first kind of way is that this micro-nano structure is micron order or nano level very little concaveconvex structure.This concaveconvex structure can increase frictional resistance, improves generating efficiency.Described concaveconvex structure can directly form when film preparation, and method that also can enough polishings makes the surface of the first high molecular polymer insulating barrier form irregular concaveconvex structure.Particularly, this concaveconvex structure can be the concaveconvex structure of semicircle, striated, cubic type, rectangular pyramid or the shape such as cylindrical.The second way is, this micro-nano structure is the poroid structure of nanoscale, now the first high molecular polymer insulating barrier material therefor is preferably Kynoar (PVDF), and its thickness is the preferred 1.0mm of 0.5-1.2mm(), and the face of its relative the second electrode is provided with a plurality of nano-pores.Wherein, the size of each nano-pore, width and the degree of depth, can select according to the needs of application, and preferred nano-pore is of a size of: width is that 10-100nm and the degree of depth are 4-50 μ m.The quantity of nano-pore can output current value and magnitude of voltage as required be adjusted, and preferably these nano-pores are that pitch of holes is being uniformly distributed of 2-30 μ m, and preferred average pitch of holes is being uniformly distributed of 9 μ m.
Lower mask body is introduced the operation principle of the nano friction generator shown in Figure 14 a and Figure 14 b.When each layer of this nano friction generator is bent downwardly, the second electrode 143 in nano friction generator produces electrostatic charge with the surperficial phase mutual friction of the first high molecular polymer insulating barrier 142, the generation of electrostatic charge can make the electric capacity between the first electrode 141 and the second electrode 143 change, thereby causes occurring electrical potential difference between the first electrode 141 and the second electrode 143.Because the first electrode 141 is connected with charging circuit module with the output electrode of the second electrode 143 as nano friction generator, and then be connected with ultracapacitor, charging circuit module and ultracapacitor form the external circuit of nano friction generator, between two output electrodes of nano friction generator, are equivalent to be communicated with by external circuit.When each layer of this nano friction generator returns to original state, the built-in potential being at this moment formed between the first electrode and the second electrode disappears, and now between Balanced the first electrode and the second electrode, will again produce reverse electrical potential difference.By repeatedly rubbing and recovering, just can in external circuit, form periodic ac signal.This ac signal is converted to DC signal after charging circuit module is processed, and this DC signal is exported to ultracapacitor and stored, thereby has realized the self-charging of ultracapacitor.
According to inventor's research, find, metal and high molecular polymer friction, the more volatile de-electromation of metal, therefore adopts metal electrode and high molecular polymer friction can improve energy output.Therefore, correspondingly, in the nano friction generator shown in Figure 14 a and Figure 14 b, the second electrode is because needs rub as friction electrode (being metal) and the first high molecular polymer, therefore its material can be selected from metal or alloy, and 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, lead alloy, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.The first electrode rubs owing to not needing, therefore, except can selecting the material of above-mentioned the second electrode of enumerating, other materials that can make electrode also can be applied, that is to say, the first electrode is except being selected from metal or alloy, and wherein metal can be Au Ag Pt Pd, aluminium, nickel, copper, titanium, chromium, selenium, iron, manganese, molybdenum, tungsten or vanadium; Alloy can be outside aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy, copper alloy, kirsite, manganese alloy, nickel alloy, lead alloy, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy, can also be selected from the nonmetallic materials such as indium tin oxide, Graphene, nano silver wire film.
The second structure of nano friction generator is as shown in Figure 15 a and Figure 15 b.Figure 15 a and Figure 15 b show respectively perspective view and the cross-sectional view of the second structure of nano friction generator.This nano friction generator comprises: the first electrode 151, the first high molecular polymer insulating barrier 152, the second high molecular polymer insulating barriers 154 and the second electrodes 153 that are cascading.Particularly, the first electrode 151 is arranged on the first side surface of the first high molecular polymer insulating barrier 152; The second electrode 153 is arranged on the first side surface of the second high molecular polymer insulating barrier 154; Wherein, the second side surface contact friction of the second side surface of the first high molecular polymer insulating barrier 152 and the second high molecular polymer insulating barrier 154 induce electric charge at the first electrode 151 and the second electrode 153 places.Wherein, the first electrode 151 and the second electrode 153 form two output electrodes of nano friction generator.
In order to improve the generating capacity of nano friction generator, at least one face in two faces that the first high molecular polymer insulating barrier 152 and the second high molecular polymer insulating barrier 154 are oppositely arranged is provided with micro-nano structure.In Figure 15 b, the face of the first high molecular polymer insulating barrier 152 is provided with micro-nano structure 155.Therefore, when nano friction generator is squeezed, apparent surface's contact friction better of the first high molecular polymer insulating barrier 152 and the second high molecular polymer insulating barrier 154, and induce more electric charge at the first electrode 151 and the second electrode 153 places.Above-mentioned micro-nano structure can, with reference to description above, repeat no more herein.
The operation principle of the nano friction generator shown in the operation principle of the nano friction generator shown in Figure 15 a and Figure 15 b and Figure 14 a and Figure 14 b is similar.Difference is only, when each layer of the nano friction generator shown in Figure 15 a and Figure 15 b is crooked, is to produce electrostatic charge by the first high molecular polymer insulating barrier 152 and the surperficial phase mutual friction of the second high molecular polymer insulating barrier 154.Therefore, the operation principle about the nano friction generator shown in Figure 15 a and Figure 15 b repeats no more herein.
Nano friction generator shown in Figure 15 a and Figure 15 b mainly produces the signal of telecommunication by the friction between polymer (the first high molecular polymer insulating barrier) and polymer (the second high molecular polymer insulating barrier).
In this structure, the first electrode and the second electrode material therefor can be indium tin oxide, Graphene, nano silver wire film, metal or alloy, and 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, lead alloy, ashbury metal, cadmium alloy, bismuth alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or tantalum alloy.
In above-mentioned two kinds of structures, the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier are selected from respectively polyimide film, aniline-formaldehyde resin film, polyformaldehyde film, ethyl cellulose film, polyamide film, melamino-formaldehyde film, polyethylene glycol succinate film, cellophane, cellulose acetate film, polyethylene glycol adipate film, polydiallyl phthalate film, fiber (regeneration) sponge film, 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 film, pet film, polyvinyl butyral film, formaldehyde phenol film, neoprene film, butadiene-propylene copolymer film, natural rubber film, polyacrylonitrile film, a kind of in 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 identical in principle, also can be different.But, if the material of two-layer high molecular polymer insulating barrier is all identical, can cause the quantity of electric charge of triboelectrification very little.Therefore preferably, the first high molecular polymer insulating barrier is different from the material of the second high molecular polymer insulating barrier.
Except above-mentioned two kinds of structures, nano friction generator can also adopt the third structure to realize, as shown in Figure 16 a and Figure 16 b.Figure 16 a and Figure 16 b show respectively perspective view and the cross-sectional view of the third structure of nano friction generator.As can be seen from the figure, the third structure has increased a thin layer between two parties on the basis of the second structure, that is: the nano friction generator of the third structure comprises the first electrode 161 of being cascading, the first high molecular polymer insulating barrier 162, thin layer 160, the second high molecular polymer insulating barrier 164 and the second electrode 163 between two parties.Particularly, the first electrode 161 is arranged on the first side surface of the first high molecular polymer insulating barrier 162; The second electrode 163 is arranged on the first side surface of the second high molecular polymer insulating barrier 164, and thin layer 160 is arranged between the second side surface of the first high molecular polymer insulating barrier 162 and the second side surface of the second high molecular polymer insulating barrier 164 between two parties.Wherein, at least one face in two faces that described thin layer between two parties 160 and the first high molecular polymer insulating barrier 162 are oppositely arranged is provided with micro-nano structure 165, and/or at least one face in two faces being oppositely arranged of described thin layer between two parties 160 and the second high molecular polymer insulating barrier 164 is provided with micro-nano structure 165, concrete set-up mode about micro-nano structure 165 can, with reference to above describing, repeat no more herein.
The material of the nano friction generator shown in Figure 16 a and Figure 16 b can be selected with reference to the material of the nano friction generator of aforesaid the second structure.Wherein, thin layer also can be selected from any one in transparent high polymer PETG (PET), dimethyl silicone polymer (PDMS), polystyrene (PS), polymethyl methacrylate (PMMA), Merlon (PC) and polymeric liquid crystal copolymer (LCP) between two parties.Wherein, the material preferably clear high polymer PETG (PET) of described the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier; Wherein, the preferred dimethyl silicone polymer of the material of described thin layer between two parties (PDMS).The first above-mentioned high molecular polymer insulating barrier, the second high molecular polymer insulating barrier, the material of thin layer can be identical between two parties, also can be different.But, if the material of three floor height Molecularly Imprinted Polymer insulating barriers is all identical, can cause the quantity of electric charge of triboelectrification very little, therefore,, in order to improve friction effect, the material of thin layer is different from the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier between two parties, the first high molecular polymer insulating barrier is preferably identical with the material of the second high molecular polymer insulating barrier, like this, can reduce material category, make making of the present invention convenient.
In the implementation shown in Figure 16 a and Figure 16 b, thin layer 160 is one layer of polymeric films between two parties, therefore similar with the implementation shown in Figure 15 a and Figure 15 b in fact, remain and generate electricity by the friction between polymer (thin layer between two parties) and polymer (the second high molecular polymer insulating barrier).Wherein, easily preparation and stable performance of thin layer between two parties.
In addition, nano friction generator can also adopt the 4th kind of structure to realize, as shown in Figure 17 a and Figure 17 b, comprise: the first electrode 171 being cascading, the first high molecular polymer insulating barrier 172, between two parties electrode layer 170, the second high molecular polymer insulating barriers 174 and the second electrode 173; Wherein, the first electrode 171 is arranged on the first side surface of the first high molecular polymer insulating barrier 172; The second electrode 173 is arranged on the first side surface of the second high molecular polymer insulating barrier 174, and electrode layer 170 is arranged between the second side surface of the first high molecular polymer insulating barrier 172 and the second side surface of the second high molecular polymer insulating barrier 174 between two parties.Wherein, the first high molecular polymer insulating barrier 172 is provided with micro-nano structure (not shown) at least one face in the face of the face of electrode layers 170 and relative the first high molecular polymer insulating barrier 172 of electrode layer 170 between two parties relatively between two parties; The second high molecular polymer insulating barrier 174 is provided with micro-nano structure (not shown) at least one face in the face of the face of electrode layers 170 and relative the second high molecular polymer insulating barrier 174 of electrode layer 170 between two parties relatively between two parties.In this mode, by rubbing between electrode layer 170 and the first high molecular polymer insulating barrier 172 and the second high molecular polymer insulating barrier 174 and produce electrostatic charge between two parties, thus will be between two parties produce electrical potential difference between electrode layer 170 and the first electrode 171 and the second electrode 173, now, the first electrode 171 and the second electrode 173 series connection are an output electrode of nano friction generator; Electrode layer 170 is another output electrode of nano friction generator between two parties.
In the structure shown in Figure 17 a and Figure 17 b, the material of the first high molecular polymer insulating barrier, the second high molecular polymer insulating barrier, the first electrode and the second electrode can be selected with reference to the material of the nano friction generator of aforesaid the second structure.Electrode layer can be selected conductive film, conducting polymer, metal material between two parties, metal material comprises simple metal and alloy, 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-alloy (aluminium alloy, titanium alloy, magnesium alloy, beryllium alloy etc.), heavy non-ferrous alloy (copper alloy, kirsite, manganese alloy, nickel alloy etc.), low-melting alloy (lead, tin, cadmium, bismuth, indium, gallium and alloy thereof), refractory alloy (tungsten alloy, molybdenum alloy, niobium alloy, tantalum alloy etc.).Preferred 100 μ m-500 μ m, more preferably 200 μ m of the thickness of electrode layer 80 between two parties.
Self-charging ultracapacitor provided by the invention can be realized self-charging function, owing to adopting flexible material, make, make crooked, the distortion arbitrarily of whole self-charging ultracapacitor, thereby make self-charging ultracapacitor of the present invention can adapt to different application occasion and environment.In addition, self-charging ultracapacitor provided by the invention can be realized the fast charging and discharging of ultracapacitor, and in discharge process, the capability retention of capacitor is high, can realize more effective discharging and recharging, and is an excellent energy storage device.Except this, the structural design of self-charging ultracapacitor provided by the invention is flexible, ingenious, and performance is better, and shape, size also can be according to user's demand processing, more facilitations.
Finally; it should be noted that: what enumerate above is only specific embodiments of the invention; certainly those skilled in the art can change and modification the present invention; if these modifications and modification all should be thought protection scope of the present invention within belonging to the scope of the claims in the present invention and equivalent technologies thereof.

Claims (25)

1. a self-charging ultracapacitor, is characterized in that, comprising:
Mechanical energy is converted to at least one nano friction generator of electric energy, each nano friction generator has two output electrodes for output electrical signals;
The charging circuit module being connected with the output electrode of described at least one nano friction generator, the signal of telecommunication of described nano friction generator output is regulated to conversion; And
Be connected with described charging circuit module, the signal of telecommunication that receives the output of described charging circuit module the ultracapacitor storing.
2. self-charging ultracapacitor according to claim 1, is characterized in that, described ultracapacitor comprises:
Substrate;
Be positioned at suprabasil barrier film, ultracapacitor the first electrode, ultracapacitor the second electrode and the first collector, the second collector, described barrier film is arranged between described ultracapacitor the first electrode and ultracapacitor the second electrode, described the first collector is connected with ultracapacitor the first electrode, described the second collector is connected with ultracapacitor the second electrode, and described charging circuit module is connected with described the first collector, the second collector;
Lay respectively at two bed course sheets on described the first collector and the second collector;
The cavity being formed by described two bed course sheets, described barrier film, described ultracapacitor the first electrode and ultracapacitor the second electrode, is filled with electrolyte in described cavity;
The encapsulated layer that described electrolyte is encapsulated.
3. self-charging ultracapacitor according to claim 2, is characterized in that, described at least one nano friction generator is arranged on a side of described ultracapacitor, and described at least one nano friction generator and described ultracapacitor share described substrate.
4. self-charging ultracapacitor according to claim 2, it is characterized in that, described at least one nano friction generator divides the both sides that are located at described ultracapacitor, be arranged at least one nano friction generator of described ultracapacitor downside and described ultracapacitor and share described substrate, be arranged between at least one nano friction generator of described ultracapacitor upside and described ultracapacitor and be also provided with insulating barrier.
5. self-charging ultracapacitor according to claim 1, is characterized in that, described ultracapacitor comprises: the first collector of parallel stacked setting, ultracapacitor the first electrode, barrier film, ultracapacitor the second electrode and the second collector successively; Described charging circuit module is connected with described the first collector, the second collector.
6. self-charging ultracapacitor according to claim 5, it is characterized in that, described at least one nano friction generator is arranged on a side of described ultracapacitor, between described at least one nano friction generator and described ultracapacitor, is also provided with insulating barrier.
7. self-charging ultracapacitor according to claim 5, it is characterized in that, described at least one nano friction generator divides the both sides that are located at described ultracapacitor, be arranged between at least one nano friction generator of described ultracapacitor downside and described ultracapacitor and be also provided with the first insulating barrier, be arranged between at least one nano friction generator of described ultracapacitor upside and described ultracapacitor and be also provided with the second insulating barrier.
8. according to the self-charging ultracapacitor described in claim 3 or 5, it is characterized in that, described nano friction generator has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.
9. according to the self-charging ultracapacitor described in claim 4 or 7, it is characterized in that:
The nano friction generator that is arranged on described ultracapacitor downside has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure;
And/or the nano friction generator that is arranged on described ultracapacitor upside has a plurality of, and arrayed is at same layer or different layers, forms parallel-connection structure.
10. according to the self-charging ultracapacitor described in claim 2 or 5, it is characterized in that, described ultracapacitor is all-solid-state supercapacitor, is selected from all solid state symmetric form Graphene ultracapacitor, all solid state symmetric form active carbon ultracapacitor, all solid state active carbon and the asymmetric ultracapacitor of metal oxide, all solid state active carbon and the asymmetric ultracapacitor of conducting polymer, all solid state active carbon and mixes a kind of in asymmetric ultracapacitor with lithium ion battery.
11. self-charging ultracapacitors according to claim 2, is characterized in that, the material of described substrate is selected from a kind of in PETG, silicon and silicon dioxide.
12. self-charging ultracapacitors according to claim 2, it is characterized in that, the material of described two bed course sheets is selected from a kind of in buna, butadiene-styrene rubber, acrylonitrile-butadiene rubber, butyl rubber, silicon rubber, polyurethane rubber, isoprene rubber, butadiene rubber, fluorubber and acrylate rubber.
13. according to the self-charging ultracapacitor described in claim 2 or 5, it is characterized in that, the material of described barrier film is autoxidation graphite; Polyvinyl alcohol-sulfuric acid system; Polyvinyl alcohol-Phosphoric Acid; 1-butyl, 3-methylimidazole bis trifluoromethyl sulfo nyl acid imide-fumed silica system; Polyaniline-1-ethyl, 3-methyl imidazolium tetrafluoroborate-trimethyl silanol system; 1-butyl, 3-methyl imidazolium tetrafluoroborate-silica gel system; Polymethyl methacrylate-ethylene carbonate-propene carbonate-lithium perchlorate system; Polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid is received system; Polyethylene glycol oxide-polyethylene glycol-trifluoromethyl sulfonic acid lithium system; A kind of in polymethyl methacrylate-ethylene carbonate-propene carbonate-perchloric acid tetraethyl ammonium system.
14. self-charging ultracapacitors according to claim 2, it is characterized in that, the material of described encapsulated layer is a kind of in aluminum plastic film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, polyformaldehyde, Merlon and polyamide membrane.
15. according to the self-charging ultracapacitor described in claim 2 or 5, it is characterized in that, the material of described the first collector and the second collector is selected from a kind of in copper, silver, al and ni; The material of described ultracapacitor the first electrode and ultracapacitor the second electrode is selected from a kind of in Graphene, active carbon, charcoal-aero gel, carbon fiber, metal oxide, conducting polymer and lithium ion battery electrode material.
16. self-charging ultracapacitors according to claim 2, it is characterized in that, described ultracapacitor the first electrode and ultracapacitor the second electrode are: parallel construction, multiple row parallel construction, interdigital structure, serpentine configuration, helical structure, dendritic structure, spiral dendritic structure or dactylotype.
17. according to the self-charging ultracapacitor described in claim 1 to 7 any one, it is characterized in that, described charging circuit module comprises:
The rectification circuit module being connected with the output electrode of at least one nano friction generator, the signal of telecommunication of described at least one nano friction generator output is carried out to rectification processing; And
Be connected with described rectification circuit module, the unidirectional pulse direct current of described rectification circuit module output carried out to filtering processing and obtain the filter circuit module of DC signal, described filter circuit module is exported to described ultracapacitor by described DC signal.
18. self-charging ultracapacitors according to claim 17, is characterized in that, described charging circuit module also comprises: charge control module and switch/voltage changing module;
Described charge control module is connected with filter circuit module, receives the DC signal of described filter circuit module output; Described charge control module is connected with described ultracapacitor, receives the charging voltage of described ultracapacitor feedback; Described charge control module is connected with described switch/voltage changing module, and described charge control module, according to described DC signal and the controlled signal of described charging voltage, is exported described control signal to described switch/voltage changing module;
Described switch/voltage changing module is connected with described filter circuit module, the DC signal of wave reception filtering circuit module output; Described switch/voltage changing module is connected with described ultracapacitor, and described switch/voltage changing module carries out switching over according to the control signal receiving and the DC signal of described filter circuit module output is carried out exporting to described ultracapacitor after transformation processing.
19. self-charging ultracapacitors according to claim 18, is characterized in that, described charging circuit module also comprises: generator control module;
Described generator control module is connected with described ultracapacitor, receives the charging voltage of described ultracapacitor feedback;
Described generator control module is connected with described nano friction generator, and described generator control module stops the signal of generating to described nano friction generator output according to described charging voltage.
20. according to the self-charging ultracapacitor described in claim 1 to 7 any one, it is characterized in that, described nano friction generator comprises: the first electrode being cascading, the first high molecular polymer insulating barrier, and the second electrode; Wherein, described the first electrode is arranged on the first side surface of described the first high molecular polymer insulating barrier; And the second side surface of described the first high molecular polymer insulating barrier is towards described the second electrode setting, and described the first electrode and the second electrode form the output electrode of described nano friction generator.
21. self-charging ultracapacitors according to claim 20, is characterized in that, described the first high molecular polymer insulating barrier is provided with micro-nano structure towards the face of the second electrode.
22. self-charging ultracapacitors according to claim 20, it is characterized in that, described nano friction generator further comprises: be arranged on the second high molecular polymer insulating barrier between described the second electrode and described the first high molecular polymer insulating barrier, described the second electrode is arranged on the first side surface of described the second high molecular polymer insulating barrier; And the second side surface of the second side surface of described the second high molecular polymer insulating barrier and described the first high molecular polymer insulating barrier is oppositely arranged.
23. self-charging ultracapacitors according to claim 22, is characterized in that, at least one face in two faces that described the first high molecular polymer insulating barrier and the second high molecular polymer insulating barrier are oppositely arranged is provided with micro-nano structure.
24. self-charging ultracapacitors according to claim 22, it is characterized in that, described nano friction generator further comprises: be arranged on the thin layer between two parties between described the first high molecular polymer insulating barrier and described the second high molecular polymer insulating barrier, wherein, described thin layer is between two parties polymer film layer, and described the first high molecular polymer insulating barrier relatively described between two parties thin layer face and thin layer between two parties with respect at least one face in the face of the first high molecular polymer insulating barrier and/or described the second high molecular polymer insulating barrier relative described between two parties at least one face in the face of thin layer and the face of relative the second high molecular polymer insulating barrier of thin layer be between two parties provided with micro-nano structure.
25. according to the self-charging ultracapacitor described in claim 1 to 7 any one, it is characterized in that, described nano friction generator comprises: the first electrode being cascading, the first high molecular polymer insulating barrier, electrode layer between two parties, the second high molecular polymer insulating barrier and the second electrode, wherein, described the first electrode is arranged on the first side surface of described the first high molecular polymer insulating barrier, described the second electrode is arranged on the first side surface of described the second high molecular polymer insulating barrier, described electrode layer is between two parties arranged between the second side surface of described the first high molecular polymer insulating barrier and the second side surface of described the second high molecular polymer insulating barrier, and described the first high molecular polymer insulating barrier relatively described between two parties electrode layer face and electrode layer between two parties with respect at least one face in the face of the first high molecular polymer insulating barrier and/or described the second high molecular polymer insulating barrier relative described between two parties at least one face in the face of electrode layer and the face of relative the second high molecular polymer insulating barrier of electrode layer be between two parties provided with micro-nano structure, after being connected with the second electrode, described the first electrode forms the output electrode of described nano friction generator with described electrode layer between two parties.
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