WO2014146501A1

WO2014146501A1 - Self-charging super capacitor

Info

Publication number: WO2014146501A1
Application number: PCT/CN2014/070174
Authority: WO
Inventors: 徐传毅; 赵豪; 吴宝荣; 郝立星
Original assignee: 纳米新能源（唐山）有限责任公司
Priority date: 2013-03-20
Filing date: 2014-01-06
Publication date: 2014-09-25
Also published as: CN104064361B; CN104064361A

Abstract

Disclosed is a self-charging super capacitor. The self-charging super capacitor comprises: at least one nanometer friction generator which is capable of converting mechanical energy into electric energy, wherein each nanometer friction generator is provided with two output electrodes which are used for outputting electrical signals; a charging circuit module which is connected to the output electrodes of the at least one nanometer friction generator and is used for adjusting and converting the electrical signals output by the nanometer friction generator; and a super capacitor which is connected to the charging circuit module and is used for receiving the electrical signals output by the charging circuit module and storing same. In the self-charging super capacitor provided in the present invention, a nanometer friction generator acts as a charging power source, and the self-charging of the super capacitor is achieved by converting mechanical energy into electric energy through the nanometer friction generator and outputting electrical signals to the super capacitor for storage after adjusting and converting same through a charging circuit module.

Description

Self-charging supercapacitor

This invention relates to the field of nanotechnology and, more particularly, to a self-charging supercapacitor.

Background technique

Supercapacitors, also known as electrochemical capacitors, are an electrochemical energy storage device between a conventional capacitor and a battery. Supercapacitors have higher electrostatic capacity than conventional capacitors; supercapacitors have higher power density and longer cycle life than batteries. Supercapacitors combine the advantages of both and are a promising energy storage device.

Existing supercapacitors are mainly composed of an electrode, an electrolyte, and a separator. The electrode includes an electrode active material and a collector. The role of the collector is to reduce the internal resistance of the electrode, requiring a large contact area with the electrode, a small contact resistance, and high corrosion resistance, stable performance in the electrolyte, and no chemical reaction.

Although the supercapacitor has superior performance, its charging power source has a single source and cannot be self-charged, so its use has certain limitations. There are also some supercapacitors in the prior art which can be prepared into a flexible structure, but the preparation process is complicated and is not easily produced by large-scale processing. As an ideal energy storage component in the future, super capacitors require a unique design. Therefore, in order to better use and apply supercapacitors, it is urgent to solve the above problems. Summary of the invention

SUMMARY OF THE INVENTION The object of the present invention is to provide a self-charging supercapacitor that achieves self-charging of a supercapacitor without the aid of an external power source, in view of the deficiencies of the prior art.

The present invention provides a self-charging supercapacitor comprising:

At least one nano-friction generator that converts mechanical energy into electrical energy, each nano-friction generator having two output electrodes for outputting electrical signals;

a charging circuit module connected to an output electrode of the at least one nano-friction generator for regulating conversion of an electrical signal output by the nano-friction generator; a super capacitor connected to the charging circuit module and receiving an electrical signal output by the charging circuit module and storing.

Optionally, the super capacitor includes: a substrate;

a separator on the substrate, a first electrode of the supercapacitor, a second electrode of the supercapacitor, and a first current collector, a second current collector; and two pad sheets on the first current collector and the second current collector, respectively;

a cavity formed by the two bedding sheets, the separator, the first electrode of the supercapacitor, and the second electrode of the supercapacitor, the cavity being filled with an electrolyte;

An encapsulation layer that encapsulates the electrolyte;

Wherein the diaphragm is disposed between the first electrode of the supercapacitor and the second electrode of the supercapacitor, the first current collector is connected to the first electrode of the supercapacitor, and the second current collector is connected to the second electrode of the supercapacitor The charging circuit module is connected to the first current collector and the second current collector.

Optionally, the at least one nano-friction generator is disposed on one side of the ultracapacitor, and the at least one nano-friction generator shares the substrate with the supercapacitor.

Optionally, the at least one nano-friction generator is disposed on two sides of the supercapacitor, and at least one nano-friction generator disposed on a lower side of the supercapacitor shares the substrate with the supercapacitor, and is disposed at the An insulating layer is further disposed between the at least one nano-friction generator on the upper side of the supercapacitor and the supercapacitor.

Optionally, the supercapacitor includes: a first current collector, a supercapacitor first electrode, a separator, a supercapacitor second electrode and a second current collector, and an encapsulation layer, which are sequentially stacked in parallel; the charging circuit module and the The first current collector and the second current collector are connected.

Optionally, the at least one nano-friction generator is disposed on one side of the ultra-capacitor, and an insulation layer is further disposed between the at least one nano-friction generator and the super capacitor.

Optionally, the at least one nano-friction generator is disposed on two sides of the ultra-capacitor, and at least one nano-friction generator disposed on a lower side of the supercapacitor is further provided with a first insulation between the super-capacitor a layer, at least one nano-friction disposed on an upper side of the supercapacitor A second insulating layer is further disposed between the generator and the super capacitor.

Optionally, the nano friction generator has multiple, and the array is arranged in the same layer or different layers to form a parallel structure.

Optionally, there are a plurality of nano-friction generators disposed on the underside of the supercapacitor, and the arrays are arranged in the same layer or different layers to form a parallel structure; and/or nano-friction disposed on the upper side of the supercapacitor There are a plurality of generators, and the arrays are arranged in the same layer or different layers to form a parallel structure.

Optionally, the supercapacitor is an all-solid supercapacitor selected from the group consisting of an all-solid symmetrical graphene supercapacitor, an all-solid symmetrical activated carbon supercapacitor, an all-solid activated carbon and a metal oxide asymmetric supercapacitor, and an all-solid activated carbon. One of a conductive type asymmetric supercapacitor, an all-solid activated carbon, and a lithium ion battery hybrid asymmetric supercapacitor.

Optionally, the material of the substrate is selected from the group consisting of polyethylene terephthalate, silicon, and silicon dioxide.

Optionally, the material of the two cushion sheets is selected from the group consisting of sodium butadiene rubber, styrene butadiene rubber, nitrile rubber, butyl rubber, silicone rubber, urethane rubber, isoprene rubber, butadiene rubber, fluororubber and acrylate. One of the rubbers.

Optionally, the material of the separator is self-oxidized graphite, polyvinyl alcohol-sulfuric acid system, polyvinyl alcohol-phosphoric acid system, 1-butyl, 3-mercaptoimidazole bistrifluorodecylsulfonyl sulfonimide- Smoke silica gel system, polyaniline-1-ethyl, 3-mercaptoimidazole tetrafluoroborate-trimethylsilyl alcohol system, 1-butyl, 3-mercaptoimidazole tetrafluoroborate-silica gel system, poly Ethyl decyl acrylate-ethylene carbonate-propylene carbonate-lithium perchlorate system, decyl methacrylate-ethylene carbonate-propylene carbonate-sodium perchlorate system, polyethylene oxide-polyethylene glycol- One of a lithium trifluoromethanelithinate system, a polydecyl methacrylate-ethylene carbonate-propylene carbonate-tetraethylammonium perchlorate system.

Optionally, the encapsulating layer is made of aluminum plastic film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer, polydecyl methacrylate, polyfluorene. One of an aldehyde, a polycarbonate, and a polyamide film.

Optionally, the materials of the first current collector and the second current collector are selected from one of copper, silver, aluminum, and nickel; the first electrode of the supercapacitor and the second electrode of the supercapacitor are selected from the group consisting of graphene , activated carbon, carbon aerogel, carbon fiber, metal oxide, conductive polymer and lithium ion battery electrode One of the materials.

Optionally, the first electrode of the supercapacitor and the second electrode of the supercapacitor are: a parallel structure, a multi-column parallel structure, an interdigitated structure, a serpentine structure, a spiral structure, a dendritic structure, a spiral dendritic structure or a fingerprint structure .

Optionally, the charging circuit module includes:

a rectifier circuit module coupled to an output electrode of the at least one nano-friction generator for rectifying an electrical signal output by the at least one nano-friction generator;

And a filter circuit module connected to the rectifier circuit module for filtering a unidirectional pulsed direct current outputted by the rectifier circuit module to obtain a direct current signal, wherein the filter circuit module outputs the direct current signal to the super capacitor.

Optionally, the charging circuit module further includes: a charging control module and a switch/transformer module; the charging control module is connected to the filter circuit module, and receives a DC signal output by the filter circuit module; the charging control module and The supercapacitor is connected to receive a charging voltage fed back by the supercapacitor; the charging control module is connected to the switch/transformer module, and the charging control module obtains a control signal according to the direct current signal and the charging voltage, Outputting the control signal to the switch/transformer module;

The switch/transformer module is connected to the filter circuit module, and receives a DC signal output by the filter circuit module; the switch/transformer module is connected to the super capacitor, and the switch/transformer module is based on the received control signal Switching is performed and the DC signal outputted by the filter circuit module is subjected to a voltage transformation process and output to the super capacitor.

Optionally, the charging circuit module further includes: a generator control module; the generator control module is connected to the super capacitor, and receives a charging voltage fed back by the super capacitor; the generator control module and the nanometer A friction generator is connected, and the generator control module outputs a signal to stop the power generation to the nano friction generator according to the charging voltage.

Optionally, the nano-friction generator includes: a first electrode, a first polymer insulating layer, and a second electrode, which are sequentially stacked; wherein the first electrode is disposed in the first polymer a first side surface of the insulating layer; and a second side surface of the first polymer insulating layer is disposed toward the second electrode, the first electrode and the second electrode constituting the nano-friction The output electrode of the generator.

Optionally, the first polymer polymer insulating layer is provided with a micro/nano structure on a surface facing the second electrode.

Optionally, the nano friction generator further includes: a second polymer insulating layer disposed between the second electrode and the first polymer insulating layer, wherein the second electrode is disposed at a first side surface of the second polymer insulating layer; and a second side surface of the second polymer insulating layer is opposite to a second side surface of the first polymer insulating layer Settings.

Optionally, at least one of the two faces disposed opposite to each of the first polymer insulating layer and the second polymer insulating layer is provided with a micro/nano structure.

Optionally, the nano-friction generator further includes: an intermediate film layer disposed between the first polymer insulating layer and the second polymer insulating layer, wherein the intermediate film layer a polymer film layer, and the first polymer polymer insulating layer is opposite to at least one of a face of the intermediate film layer and an intermediate film layer with respect to a face of the first polymer polymer insulating layer and/or The second polymer insulating layer is provided with a micro/nano structure on at least one of a surface of the intermediate film layer and a surface of the intermediate film layer and the second polymer insulating layer.

Optionally, the nano-friction generator includes: a first electrode, a first polymer insulating layer, an intervening electrode layer, a second polymer insulating layer, and a second electrode; a first electrode is disposed on the first side surface of the first polymer insulating layer; the second electrode is disposed on the first side surface of the second polymer insulating layer, the intervening electrode a layer is disposed between the second side surface of the first polymer insulating layer and the second side surface of the second polymer insulating layer, and the first polymer insulating layer is opposite a surface of the intervening electrode layer and at least one of a surface of the intervening electrode layer with respect to the first polymer insulating layer and/or a surface of the second polymer insulating layer with respect to the intervening electrode layer The intervening electrode layer is provided with a micro/nano structure on at least one of the faces of the second polymer insulating layer, and the first electrode and the second electrode are connected to form the nano-friction with the intervening electrode layer Motor output electrode.

In the self-charging supercapacitor provided by the present invention, the nano-friction generator functions as a charging power source, which converts the mechanical energy into electrical energy, and then adjusts the electric energy signal by the charging circuit module. The section is converted and output to the supercapacitor for storage, thereby realizing self-charging of the supercapacitor. BRIEF abstract

1 is a block diagram showing the principle structure of a self-charging supercapacitor provided by the present invention;

2 is a schematic perspective view of a first embodiment of a self-charging supercapacitor according to the present invention; FIG. 3 is a schematic cross-sectional view of a first embodiment of a self-charging supercapacitor according to the present invention; FIG. 4a to FIG. a schematic plan view of the structure between the second electrode of the supercapacitor;

5 is a schematic diagram of a circuit principle of a first embodiment of a self-charging supercapacitor provided by the present invention;

FIG. 6 is another schematic diagram of the circuit principle of the first embodiment of the self-charging supercapacitor provided by the present invention; FIG.

Figure 7 is a schematic view showing a plurality of nano-friction generators arranged side by side in the same layer;

8 is a schematic perspective view of a second embodiment of a self-charging supercapacitor provided by the present invention; FIG. 9 is a cross-sectional view of a second embodiment of a self-charging supercapacitor provided by the present invention; FIG. 10 is a self-charging supercapacitor provided by the present invention. FIG. 11 is a schematic cross-sectional view of a third embodiment of a self-charging supercapacitor according to the present invention; FIG. 12 is a schematic perspective view of a fourth embodiment of a self-charging supercapacitor provided by the present invention; A cross-sectional view of a fourth embodiment of a self-charging supercapacitor provided by the present invention; FIGS. 14a and 14b are respectively a perspective structural view and a cross-sectional structural view of a first structure of a nano-friction generator;

15a and 15b respectively show a schematic perspective view and a cross-sectional structural view of a second structure of a nano-friction generator;

16a and 16b respectively show a schematic perspective view and a cross-sectional structural view of a third structure of a nano-friction generator;

17a and 17b are respectively a perspective structural view and a cross-sectional structural view showing a fourth structure of a nano-friction generator. Preferred embodiment of the invention

The present invention will be described in detail by the following detailed description of the preferred embodiments of the invention, but the invention is not limited thereto.

1 is a block diagram showing the principle structure of a self-charging supercapacitor provided by the present invention. As shown in FIG. 1, the self-charging supercapacitor includes a nano-friction generator 11, a charging circuit module 12, and a supercapacitor 13. Figure 1 is only a schematic diagram. In practice, a self-charging supercapacitor may include one or more nano-friction generators, each having two output electrodes for outputting electrical signals. The output electrode of the nano-friction generator 11 is connected to the charging circuit module 12, and the charging circuit module 12 is connected to the supercapacitor 13. The basic working principle of the self-charging supercapacitor is: under the action of an external force, the nano-friction generator 11 undergoes mechanical deformation to convert mechanical energy into electrical energy; after that, the output electrode of the nano-friction generator 11 outputs an electrical signal to the charging circuit module. 12; The charging circuit module 12 adjusts and converts the electrical signal to output to the ultracapacitor 13, and the supercapacitor 13 receives the adjusted converted electrical signal and stores it for use by an external electrical device.

In the self-charging supercapacitor provided by the embodiment, the nano-friction generator functions as a charging power source, and converts the mechanical energy into electrical energy, and then the charging circuit module adjusts and converts the electric energy signal to output to the supercapacitor for storage. Thereby self-charging of the supercapacitor is achieved. FIG. 2 is a schematic perspective structural view of a first embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 2, the self-charging supercapacitor includes: a supercapacitor 21 and a nano-friction generator 22 disposed on one side of the supercapacitor 21. Wherein, the nano friction generator 22 is placed on the bottom layer, the super capacitor 21 is disposed on the upper surface of the nano friction generator 22, and the nano friction generator 22 is formed integrally with the super capacitor 21. The charging circuit module is not shown in FIG. The two output electrodes of the nano-friction generator 22 are connected to the charging circuit module, and the charging circuit module is connected to the supercapacitor 21 to realize the storage of electric energy.

In this embodiment, the ultracapacitor 21 is an all-solid supercapacitor selected from the group consisting of an all-solid symmetrical graphene supercapacitor, an all-solid symmetrical activated carbon supercapacitor, an all-solid activated carbon and a metal oxide asymmetric supercapacitor, and an all-solid activated carbon. One of a conductive type asymmetric supercapacitor, an all-solid-state activated carbon, and a lithium ion battery hybrid asymmetric supercapacitor. Preferably, the ultracapacitor 21 is selected from an all solid state symmetrical graphene supercapacitor. 3 is a schematic cross-sectional view showing a first embodiment of a self-charging supercapacitor provided by the present invention. Referring to FIG. 3, the structure of the supercapacitor is illustrated by taking an all-solid-state symmetrical graphene supercapacitor as an example. As shown in FIG. 3, the supercapacitor includes: a substrate 31, a diaphragm 32 on the substrate 31, a supercapacitor first electrode 33, a supercapacitor second electrode 34, a first current collector 35, a second current collector 36, and two pads. The layer 37, a cavity 38 filled with an electrolyte, and an encapsulation layer 39 for encapsulating the electrolyte. Wherein the separator 32 is graphite oxide, the supercapacitor first electrode 33 and the supercapacitor second electrode 34 are graphene, and the first current collector 35 and the second current collector 36 are metal strips. The diaphragm 32 is disposed between the supercapacitor first electrode 33 and the supercapacitor second electrode 34. In FIG. 3, the supercapacitor first electrode 33 and the supercapacitor second electrode 34 are located on both sides of the diaphragm 32; the first current collector 35 passes through the conductive paste Connected to the supercapacitor first electrode 33, the second current collector 36 is connected to the supercapacitor second electrode 34 via a conductive paste. In FIG. 3, the first current collector 35 is located outside the supercapacitor first electrode 33, and the second current collector 36 is located. The outer side of the second capacitor 34 of the supercapacitor. Two cushion sheets 37 are provided on the two current collectors, and the two cushion sheets 37, the diaphragm 32, the supercapacitor first electrode 33 and the supercapacitor second electrode 34 are formed with a cavity 38 for filling the electrolysis liquid. The encapsulation layer 39 encapsulates the electrolyte to form a very thin supercapacitor.

The nano-friction generator in Fig. 3 is a layered structure including: a friction electrode 30A, a polymer polymer insulating layer 30B, and an electrode 30C. The nano friction generator and the super capacitor share the substrate 31. The structure of the nano-friction generator will be described in detail later.

In this embodiment, the material of the substrate 31 is selected from one of polyethylene terephthalate (PET), silicon (Si), and silicon dioxide (SiO ₂ ).

The material of the first current collector 35 and the second current collector 36 is selected from one of copper, silver, aluminum and nickel. Specifically, when the PVA system is used as an electrolyte, it may be copper or silver, etc., and is used as an electrolysis in an ionic liquid system. The liquid may be aluminum or nickel.

The material of the supercapacitor first electrode 33 and the supercapacitor second electrode 34 is selected from the group consisting of graphene, activated carbon, carbon aerogel, carbon fiber, metal oxide, conductive polymer, and lithium ion battery electrode material.

The material of the separator 32 may be selected from the group consisting of graphite oxide, PVA-H ₂ S0 ₄ (polyvinyl alcohol-sulfuric acid) system, PVA-H ₃ P0 ₄ (polyvinyl alcohol-phosphoric acid) system, 1-butyl, 3-mercaptoimidazole. Bis-trifluorofluorenyl sulfonylurea-smoke silica system, PAN-[EMIm]BF ₄ -TMS (polyaniline-1-ethyl, 3-mercaptoimidazole Tetrafluoroborate-trimethylsilyl alcohol) system, 1-butyl, 3-mercaptoimidazole tetrafluoroborate-silica gel system, PMMA-EC-PC-LiC10 ₄ (polydecyl acrylate-carbonate) Vinyl ester-propylene carbonate-lithium perchlorate system, PMMA-EC-PC-NaC10 ₄ (poly(mercapto acrylate-ethylene carbonate-propylene carbonate-sodium perchlorate) system, PEO-PEG-LiCF ₃ S0 ₃ (polyethylene oxide-polyethylene glycol-trifluoromethanesulfonate lithium) system, PMMA-EC-PC-TEAC10 ₄ (polydecyl methacrylate-ethylene carbonate-propylene carbonate-perchloric acid One of the tetraethylammonium) systems.

The material of the two cushion sheets 37 is selected from the group consisting of sodium butadiene rubber, styrene butadiene rubber, nitrile rubber, butyl rubber, silicone rubber, urethane rubber, isoprene rubber, butadiene rubber, fluororubber and acrylate rubber. .

The electrolyte is solid or colloidal. The electrolyte system is PVA-H ₂ S0 ₄ (polyvinyl alcohol-sulfuric acid) system, PVA-3⁄4P0 ₄ (polyvinyl alcohol-phosphoric acid) system, 1-butyl, 3-fluorenyl Imidazole bistrifluorodecylsulfonylsulfonimide-smoke silica gel system, PAN-[EMIm]BF ₄ -TMS (polyaniline-1-ethyl, 3-mercaptoimidazole tetrafluoroborate-trimethylsilyl) Alcohol) system, 1-butyl, 3-mercaptoimidazole tetrafluoroborate-silica gel system, PMMA-EC-PC-LiC10 ₄ (polydecyl methacrylate-ethylene carbonate-propylene carbonate-perchloric acid Lithium) system, PMMA-EC-PC-NaC10 ₄ (poly(alkyl acrylate-ethylene carbonate-propylene carbonate-sodium perchlorate) system, PEO-PEG-LiCF ₃ S0 ₃ (polyethylene oxide-polyethylene) a diol-lithium trifluoromethanesulfonate system, one of PMMA-EC-PC-TEAC10 ₄ (poly(mercapto acrylate-ethylene carbonate-propylene carbonate-tetraethylammonium perchlorate) system .

The encapsulating layer 39 is made of aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS). One of polydecyl methacrylate (PMMA), polyacetal (POM), polycarbonate (PC), and polyamide (PA).

In this embodiment, there may be various structures between the first electrode of the supercapacitor and the second electrode of the supercapacitor, and FIGS. 4a to 4h are schematic plan views of the structure between the first electrode of the supercapacitor and the second electrode of the supercapacitor. 4a shows a parallel structure in which the supercapacitor first electrode 41A and the supercapacitor second electrode 41B are parallel with a diaphragm 41C therebetween. Figure 4b shows a multi-column parallel structure in which the electrodes 42A have multiple columns and are parallel to each other. Fig. 4c shows an interdigitated structure in which a separator 43C is provided between the supercapacitor first electrode 43A and the supercapacitor second electrode 43B, and such an interdigitated structure is shown in Fig. 3. Figure 4d shows a serpentine structure, supercapacitor A separator is provided between the one electrode 44A and the second electrode 44B of the supercapacitor. Fig. 4e shows a spiral structure, and a separator between the supercapacitor first electrode 45A and the supercapacitor second electrode 45B. Figure 4f shows a dendritic structure with a separator between the supercapacitor first electrode 46A and the supercapacitor second electrode 46B. Figure 4g shows a spiral dendritic structure with a separator between the supercapacitor first electrode 47A and the supercapacitor second electrode 47B. Figure 4h shows the fingerprint structure, with the separator between the supercapacitor first electrode 48A and the supercapacitor second electrode 48B.

The above all-solid-state symmetrical graphene supercapacitor is preferably prepared by a laser method, and the steps thereof include:

(1) sticking a substrate (such as PET) to the optical disc;

(2) A method for preparing an aqueous graphite oxide solution (10-10 mg/ml, graphite oxide)

The Hummers method is applied dropwise onto a PET substrate to dry the moisture leaving the golden brown graphite oxide;

(3) putting the above-mentioned optical disc into a dvd recorder, and performing structural fabrication to form a black graphene structure;

(4) pasting the copper strip current collector with conductive silver glue on both sides of the graphene structure;

(5) placing a backing cushion for sealing on the basis of the step (4);

(6) dropping a colloidal electrolyte into the backing cushion layer and evaporating the water;

(7) The overall package yields a flexible solid electrolyte supercapacitor.

Due to the uncertainty of the external force acting on the nano-friction generator, the magnitude of the alternating current generated by the nano-friction generator is also uncertain. For example, a single nano-friction generator can output a voltage of several volts to several kilovolts under external force tapping. This particularity requires a reasonable design of the external circuit to achieve a stable output. The invention adjusts and converts the electrical signal outputted by the nano friction generator through the charging circuit module to achieve stable output. FIG. 5 is a schematic diagram of a circuit principle of a first embodiment of a self-charging supercapacitor provided by the present invention. Fig. 5 shows the internal structure of the charging circuit module and its connection relationship with the nano-friction generator and the supercapacitor. As shown in FIG. 5, the charging circuit module includes: a rectifier circuit module 51 and a filter circuit module 52. The rectifier circuit module 51 is connected to the output electrode of the at least one nano-friction generator, and performs rectification processing on the electrical signal output by the at least one nano-friction generator. Specifically, the two input ends 51A and 51B of the rectifier circuit module 51 are respectively connected to the two of the nano friction generators 53. The output electrodes receive the electrical signals output by the nano-friction generator 53. For a structure comprising a plurality of nano-friction generators, the two output electrodes of the plurality of nano-friction generators are connected in parallel and then connected to the two input terminals 51A and 51B of the rectifier circuit module 51.

The two output terminals 51C and 51D of the rectifier circuit module 51 are connected to the filter circuit module 52, and the rectifier circuit module 51 outputs the one-way pulsed direct current obtained by rectifying the electrical signal output from the nano-friction generator 53 to the filter circuit module 52. The filter circuit module 52 is connected to the super capacitor 54. The filter circuit module 52 filters the unidirectional pulse DC output from the rectifier circuit module 51 to obtain a DC signal to be output to the super capacitor 54.

As shown in Fig. 5, the filter circuit module 52 has two terminals. Specifically, the first end 52A of the filter circuit module 52 is connected to the output terminal 51D of the rectifier circuit module 51, and the second end 52B of the filter circuit module 52 is connected to the output terminal 51C of the rectifier circuit module 51. The first end 52A of the filter circuit module 52 is fluidly coupled to the first current collector of the supercapacitor, and the second end 52B of the filter circuit module 52 is coupled to the second current collector of the supercapacitor. In a practical application, the second end 52B of the filter circuit module 52 is typically grounded.

For the circuit shown in Fig. 5, when an external force acts on the nano-friction generator, the nano-friction generator is mechanically deformed, thereby generating an alternating pulse electric signal. The pulsed electrical signal of the alternating current is first input to the rectifier circuit module, and is rectified by the rectifier circuit module to obtain a unidirectional pulsating direct current. The one-way pulsating direct current is input to the filter circuit module for filtering, and the interference clutter in the unidirectional pulsating direct current is filtered to obtain a direct current signal. Finally, this DC signal is directly input to the supercapacitor for charging. Here you can charge one supercapacitor or multiple supercapacitors in parallel.

The advantages of the above circuit are: (1) According to the size of the electric energy generated by the nano-friction generator and the size of the supercapacitor capacitor and the charging voltage, by adjusting the relevant parameters of the filter circuit module, the maximum utilization of the nano-friction generator can be utilized. Electrical energy, improve energy conversion efficiency; (2) Depending on the application environment, the nano-friction generator generates a wide range of voltage amplitudes, which can be adjusted to the voltage charged by the supercapacitor by adjusting the relevant parameters of the filter circuit module. Overcoming the uncertainty of the voltage generated by the nano-friction generator.

Further, the charging circuit module can also adopt a more preferable structure. FIG. 6 is another schematic diagram of the circuit principle of the first embodiment of the self-charging supercapacitor provided by the present invention. Figure 6 shows The internal structure of the preferred charging circuit module and its connection relationship with the nano-friction generator and the supercapacitor. As shown in FIG. 6, the charging circuit module includes a charging control module 63 and a switching/transforming module 64 in addition to the rectifier circuit module 61 and the filter circuit module 62. The functions of the rectifier circuit module 61 and the filter circuit module 62 are described above, and are not described again.

The charging control module 63 is connected to the filter circuit module 62, and receives the DC voltage signal U1 outputted by the filter circuit module 62. The charging control module 63 is connected to the super capacitor 65, and receives the charging voltage U fed back by the super capacitor 65. The charging voltage U is super. The voltage signal formed between the two current collectors of the capacitor 65; the charging control module 63 is also connected to the switch/transformer module 64, and the charging control module 63 obtains a control signal according to the DC voltage signal U1 and the charging voltage U, to switch/transform Module 64 outputs a control signal. The switch/transformer module 64 is connected to the filter circuit module 62, and receives the DC voltage signal U1 output by the filter circuit module 62. The switch/transformer module 64 is also connected to the super capacitor 65, and the switch/transformer module 64 performs the control signal according to the received control signal. The switching and switching of the DC voltage signal output from the filter circuit module 62 are adjusted to accommodate the voltage U2 that charges the supercapacitor 65.

For the circuit shown in FIG. 6, the difference from FIG. 5 is that the DC voltage signal U1 obtained by the filtering process is input to the charging control module 63, and the charging control module 63 determines the time according to the magnitude of the DC voltage signal U1. The supercapacitor 65 is charged; and the state of charge of the supercapacitor 65 is closely monitored, and the switch/transformer module 64 is controlled in accordance with the state of charging of the supercapacitor 65. The output voltage of the filter circuit module 62 is a gradually increasing output voltage. This output voltage is increased to the voltage limiting voltage. This voltage limiting voltage is a circuit protection voltage to prevent the circuit from being damaged due to excessive voltage.

Since the entire charging circuit module has no external power supply, the charging control module 63 controls the switching/transforming module 64 to charge the super capacitor 65. The operating power source is also derived from the nano-friction generator, so a charging control module 63 is specifically provided. The startup voltage, after the output voltage of the filter circuit module 62 reaches the startup voltage, the charging control module 63 drives the switch/transformer module 64 to initiate charging.

Another function of the charging control module 63 is to adjust the DC voltage signal U1 according to the size of the filtered DC voltage signal U1 and the charging voltage U of the supercapacitor 65, and adjust to the voltage U2 for charging the super capacitor 65, and Selective drive switch / transformer module 64 The supercapacitor 65 is charged.

According to C=Q U, the capacity C of the supercapacitor is a fixed value. During the charging of the supercapacitor, the amount of charge Q is constantly increasing, and the voltage U of the supercapacitor is constantly rising. In order to charge the supercapacitor more efficiently, the charging control module 63 adjusts the circuit in the switch/transformer module 64 based on the charging voltage U fed back by the supercapacitor 65 and the numerical value of the DC voltage signal U1 outputted by the filter circuit module 62. The conversion of the voltages U1 to U2 yields the real-time charging voltage U2 of the supercapacitor 65. There is a corresponding charging match between U2 and U to ensure the highest energy conversion efficiency. For example, assuming that the full voltage of the supercapacitor 65 is U0, the charging control module 63 compares the charging voltage U fed back by the supercapacitor 65 with U0. If U is less than U0, it indicates that the supercapacitor 65 is not fully charged and needs to continue charging; U is equal to U0, indicating that the supercapacitor 65 is full. At the same time, the charging control module 63 compares the DC voltage signal U1 outputted by the filter circuit module 62 with U0. If U1 is greater than U0, the charging control module 63 outputs a control signal to control the switch/transformer module 64 to perform step-down processing on U1. The real-time charging voltage U2 of the supercapacitor 65; if U1 is less than U0, the charging control module 63 outputs a control signal to control the switching/transforming module 64 to perform a step-up process on U1 to obtain a real-time charging voltage U2 of the supercapacitor 65.

Here you can charge one supercapacitor or multiple supercapacitors, as shown in Figure 6, which shows three supercapacitors, which are connected in parallel. When charging multiple supercapacitors, you can fill them one by one or at the same time. The charging by one is achieved by the following: The charging control module 63 compares the charging voltage U fed back by the currently charging supercapacitor with its full voltage U0, and if U has reached U0, the charging control module 63 outputs a control signal to control the switching/changing The voltage module 64 switches the switch to the next supercapacitor and continues to charge the next supercapacitor.

Further, to protect the nano-friction generator, the charging circuit module may further include a generator control module 66. The generator control module 66 is coupled to the supercapacitor 65 to receive a charging voltage U fed back by the supercapacitor 65, the charging voltage U being a voltage signal formed between the two current collectors of the supercapacitor 65; the generator control module 66 is also The nano-friction generator is connected to output a signal to stop the power generation to the nano-friction generator. When the supercapacitor 65 is full, a full voltage is obtained, which is fed back to the generator control module 66, and the generator control module 66 will The m friction generator is turned off, thereby stopping power generation.

The advantages of the circuit shown in Figure 6 are: (1) Due to the uncertainty of the external force acting on the nano-friction generator, the magnitude of the alternating current generated by the nano-friction generator is also uncertain, and the circuit can convert the uncertain voltage value. It is suitable for the charging voltage of supercapacitor and has strong adaptability. It expands the application field of self-charging supercapacitor; (2) Because the charging control module is specially designed in the circuit, the charging voltage is adjusted according to the real-time voltage of the supercapacitor, making super The real-time voltage of the capacitor maintains a dynamic matching relationship with the charging voltage, so that the electric energy emitted by the nano-friction generator is maximized to the supercapacitor, and the maximum energy storage effect is achieved; (3) according to the filling of the supercapacitor, The generator control module controls the operation of the nano-friction generator to extend the service life of the nano-friction generator; (4) When charging multiple supercapacitors, one of them will automatically switch to the next supercapacitor when it is full. Charging.

The self-charging supercapacitor provided by the embodiment is not limited to including a single nano-friction generator, and a plurality of nano-friction generators may be disposed on one side of the supercapacitor. Specifically, there are a plurality of nano-friction generators disposed on one side of the super capacitor, and the arrays of the nano-friction generators are arranged in the same layer or different layers, and their corresponding output electrodes are connected together to form a parallel structure. The arrangement can be seen in Figure 7. Compared with the characteristics of large voltage and small current generated by a single nano-friction generator, multiple parallel nano-friction generators can increase the current output to achieve better charging effect; and because of multiple nano-friction generators Evenly arranged, it can make it evenly stressed and has a good linear superposition effect.

FIG. 8 is a schematic perspective structural view of a second embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 8, the self-charging supercapacitor includes: a supercapacitor 81 and nano-friction generators 82 and 83 disposed on both sides of the supercapacitor 81, similar to a "sandwich" structure. Among them, the nano friction generator 82 is disposed on the lower side of the super capacitor 81, and the nano friction generator 83 is disposed on the upper side of the super capacitor 81. The supercapacitor 81 is formed integrally with the nano friction generators 82 and 83 on the upper and lower sides. The charging circuit module is not shown in FIG. The two output electrodes of the nano-friction generators 82 and 83 are connected in parallel to the charging circuit module, and the charging circuit module is connected to the two current collectors of the super capacitor 81 to realize the storage of electric energy.

In this embodiment, the supercapacitor 81 is an all-solid supercapacitor selected from the group consisting of an all-solid symmetrical graphene supercapacitor, an all-solid symmetrical activated carbon supercapacitor, an all-solid activated carbon and a metal. One of an asymmetric asymmetric supercapacitor, an all-solid activated carbon and a conductive polymer asymmetric supercapacitor, an all-solid activated carbon and a lithium ion battery hybrid asymmetric supercapacitor. Preferably, the ultracapacitor 81 is selected from an all solid state symmetrical graphene supercapacitor.

FIG. 9 is a schematic cross-sectional view showing a second embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 9, the structure of the supercapacitor 81 is the same as that described in the first embodiment, and the materials which are included in the device are also the same as those described in the first embodiment, and will not be described again. The nano-friction generators 82 and 83 are layered and will be described in detail later. The nano-friction generator 82 shares a substrate with the supercapacitor 81, and an insulating layer 90 is further disposed between the nano-friction generator 83 and the supercapacitor 81. It should be noted here that when the nano-friction generator and the super-capacitor share the substrate, there is no need to add a barrier layer. When the nano-friction generator and the supercapacitor do not share a substrate, an insulating layer is needed to prevent conduction.

The charging circuit module in this embodiment is also the same as that described in the first embodiment, and will not be described again.

The self-charging supercapacitor provided in this embodiment is not limited to including two upper and lower nano-friction generators, and a plurality of nano-friction generators may be disposed on the upper side and/or the lower side of the supercapacitor, specifically, disposed on the underside of the supercapacitor There may be multiple nano-friction generators, and the arrays are arranged in the same layer or different layers to form a parallel structure; and/or, there may be multiple nano-friction generators disposed on the upper side of the supercapacitor, and the arrays are arranged in the same layer. Or different layers, forming a parallel structure. The arrangement can be referred to Figure 7. A plurality of nano-friction generators connected in parallel can increase the output of current to achieve better charging effect; and because a plurality of nano-friction generators are evenly arranged, the force can be uniform and have a good linear superposition effect.

FIG. 10 is a schematic perspective structural view of a third embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 10, the self-charging supercapacitor includes: a supercapacitor 101 and a nano-friction generator 102 disposed on the side of the supercapacitor 101, and an insulating layer 103 is further disposed between the nano-friction generator 102 and the ultracapacitor 101. The nano-friction generator 102 is placed on the bottom layer, the insulating layer 103 is located on the upper surface of the nano-friction generator 102, and the supercapacitor 101 is located on the upper surface of the insulating layer 103. The supercapacitor 101, the insulating layer 103, and the nano-friction generator 102 are formed in one piece. The charging circuit module is not shown in FIG. The two output electrodes of the nano-friction generator 102 are connected to the charging circuit module, and the charging circuit module is further connected to the two current collectors of the super capacitor 101. Thereby realizing the storage of electrical energy.

In this embodiment, the supercapacitor 101 is an all-solid supercapacitor selected from the group consisting of a fully solid symmetrical graphene supercapacitor, an all solid state symmetrical activated carbon supercapacitor, an all solid activated carbon and a metal oxide asymmetric supercapacitor, and an all solid activated carbon. One of asymmetrical supercapacitors mixed with a conductive polymer asymmetric supercapacitor, an all solid state activated carbon, and a lithium ion battery. Preferably, the ultracapacitor 101 is selected from an all solid state symmetrical graphene supercapacitor.

11 is a schematic cross-sectional view showing a third embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 11, the supercapacitor includes: a first current collector 111, a supercapacitor first electrode 112, a separator 113, a supercapacitor second electrode 114, and a second current collector 115 which are sequentially stacked in parallel, and the supercapacitor further includes a package. Layer (not shown in Figure 11). The insulating layer 103 is in contact with the first current collector 111. The nano-friction generator 102 in Fig. 11 is a layered structure, and its specific structure will be described in detail later.

In this embodiment, the materials of the first current collector 111 and the second current collector 115 are selected from one of copper, silver, aluminum, and nickel.

The material of the supercapacitor first electrode 112 and the supercapacitor second electrode 114 is selected from the group consisting of graphene, activated carbon, carbon aerogel, carbon fiber, metal oxide, conductive polymer, and lithium ion battery material.

The material of the separator 113 may be selected from the group consisting of graphite oxide, PVA-H ₂ S0 ₄ (polyvinyl alcohol-sulfuric acid) system, PVA-H ₃ P0 ₄ (polyvinyl alcohol-phosphoric acid) system, 1-butyl, 3-mercaptoimidazole Bis-trifluorofluorenyl sulfonyl imide-smoke silica gel system, PAN-[EMIm]BF ₄ -TMS (polyaniline-1-ethyl, 3-mercaptoimidazole tetrafluoroborate-tridecylsilanol System, 1-butyl, 3-mercaptoimidazole tetrafluoroborate-silica gel system, PMMA-EC-PC-LiC10 ₄ (polydecyl methacrylate-ethylene carbonate-propylene carbonate-lithium perchlorate) System, PMMA-EC-PC-NaC10 ₄ (poly(decyl methacrylate-ethylene carbonate-propylene carbonate-sodium perchlorate) system, PEO-PEG-LiCF ₃ S0 ₃ (polyethylene oxide-polyethylene) One of the alcohol-trifluoromethanesulfonate lithium) system, PMMA-EC-PC-TEAC104 (poly(mercapto acrylate-ethylene carbonate-propylene carbonate-tetraethylammonium perchlorate) system.

The electrolyte is solid or colloidal, the electrolyte system is PVA-H ₂ S0 ₄ (polyvinyl alcohol-sulfuric acid) system; PVA-3⁄4P0 ₄ (polyvinyl alcohol-phosphoric acid) system, 1-butyl, 3-fluorenyl Imidazole bistrifluorodecylsulfonylsulfonimide-smoke silica gel system, PAN-[EMIm]BF ₄ -TMS (polyaniline-1-ethyl, 3-oxime) Imidazolium tetrafluoroborate-trimethylsilyl alcohol) system, 1-butyl, 3-mercaptoimidazole tetrafluoroborate-silica gel system, PMMA-EC-PC-LiC10 ₄ (polydecyl methacrylate) -ethylene carbonate-propylene carbonate-lithium perchlorate system, PMMA-EC-PC-NaC10 ₄ (poly(mercapto acrylate-ethylene carbonate-propylene carbonate-sodium perchlorate) system, PEO-PEG -LiCF ₃ S0 ₃ (polyethylene oxide-polyethylene glycol-trifluoromethanelithinate) system, PMMA-EC-PC-TEAC10 ₄ (poly(mercapto acrylate)-ethylene carbonate-propylene carbonate-high One of the tetraethylammonium chlorate systems.

The encapsulating layer is made of aluminum plastic film, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), One of polydecyl methacrylate (PMMA), polyfurfural (POM), polycarbonate (PC), and polyamide (PA).

The charging circuit module in this embodiment is also the same as that described in the first embodiment, and will not be described again. The charging circuit module is coupled to the first current collector 111 and the second current collector 115 described above.

The self-charging supercapacitor provided in this embodiment is not limited to including a single nano-friction generator, and a plurality of nano-friction generators may be disposed on one side of the super-capacitor. Specifically, how many nano-friction generators are disposed on one side of the supercapacitor The nano-friction generator arrays are arranged in the same layer or different layers, and their corresponding output electrodes are connected together to form a parallel structure. The arrangement can be seen in Figure 7. Compared with the characteristics of large voltage and small current generated by a single nano-friction generator, multiple parallel nano-friction generators can increase the current output to achieve better charging effect; and because of multiple nano-friction generators Evenly arranged, it can make it evenly stressed and has a good linear superposition effect.

FIG. 12 is a schematic perspective structural view of a fourth embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 12, the self-charging supercapacitor includes: a supercapacitor 121 and nano-friction generators 122 and 123 disposed on both sides of the supercapacitor 121. The nano-friction generator 122 is disposed on the lower side of the supercapacitor 121, and the first insulating layer 124 is further disposed between the nano-friction generator 122 and the ultra-capacitor 121. The nano-friction generator 123 is disposed on the upper side of the supercapacitor 121. A second insulating layer 125 is further disposed between the nano friction generator 123 and the ultracapacitor 121. The supercapacitor 121 is formed integrally with the nano friction generators 122 and 123 on the upper and lower sides, and the first insulating layer 124 and the second insulating layer 125. The charging circuit module is not shown in FIG. The two output electrodes of the nano friction generators 122 and 123 are connected in parallel to the charging circuit module, and the charging circuit The module is then coupled to the two current collectors of the supercapacitor 121 to effect storage of electrical energy.

In this embodiment, the supercapacitor 121 is an all-solid supercapacitor selected from the group consisting of an all-solid symmetrical graphene supercapacitor, an all-solid symmetrical activated carbon supercapacitor, an all-solid activated carbon and a metal oxide asymmetric supercapacitor, and an all-solid activated carbon. One of a conductive type asymmetric supercapacitor, an all-solid-state activated carbon, and a lithium ion battery hybrid asymmetric supercapacitor. Preferably, the ultracapacitor 121 is selected from an all solid state symmetrical graphene supercapacitor.

FIG. 13 is a schematic cross-sectional view showing a fourth embodiment of a self-charging supercapacitor provided by the present invention. As shown in FIG. 13, the structure of the supercapacitor 121 is the same as that described in the third embodiment, and the materials which are included in the device are also the same as those described in the third embodiment, and are not described herein again. The nano-friction motors 122 and 123 are layered and will be described in detail later. A first insulating layer 124 is disposed between the nano-friction generator 122 and the ultracapacitor 121, and a second insulating layer 125 is disposed between the nano-friction generator 123 and the super-capacitor 121.

The structure and working principle of the nano-friction generator in self-charging supercapacitors will be described in detail below.

The first structure of the nano-friction generator is shown in Figures 14a and 14b. 14a and 14b are respectively a perspective structural view and a cross-sectional structural view showing a first structure of a nano-friction generator. The nano-friction generator includes: a first electrode 141, a first polymer insulating layer 142, and a second electrode 143 which are sequentially stacked. Specifically, the first electrode 141 is disposed on the first side surface of the first polymer insulating layer 142; and the first polymer insulating layer 142 The second side surface is in frictional contact with the surface of the second electrode 143 and induces a charge at the second electrode and the first electrode. Therefore, the first electrode 141 and the second electrode 143 described above constitute two output electrodes of the nano friction generator.

In order to increase the power generation capability of the nano-friction generator, a micro-nano structure 144 is further provided on the second side surface of the first polymer insulating layer 142 (i.e., the surface opposite to the second electrode 143). Therefore, when the nano-friction generator is pressed, the opposing surfaces of the first polymer-polymer insulating layer 142 and the second electrode 143 can better contact the friction and are induced at the first electrode 141 and the second electrode 143. More charge. Since the second electrode 143 is mainly used for rubbing with the first polymer polymer insulating layer 142, the second electrode 143 may also be referred to as a friction electrode.

The micro-nano structure 144 can adopt the following two possible implementation manners: In the first method, the micro-nano structure is a very small concave-convex structure of a micrometer or a nanometer. The uneven structure can increase frictional resistance and improve power generation efficiency. The uneven structure can be formed directly at the time of film preparation, and the surface of the first polymer insulating layer can be formed into an irregular concave-convex structure by a grinding method. Specifically, the uneven structure may be a concave-convex structure of a semicircular shape, a striped shape, a cubic shape, a quadrangular pyramid shape, or a cylindrical shape. In the second mode, the micro/nano structure is a nano-scale pore structure, and the material used for the first polymer insulating layer is preferably polyvinylidene fluoride (PVDF), and the thickness thereof is 0.5-1.2 mm (preferably 1.0 mm). And a plurality of nanopores are disposed on a surface of the second electrode. The size of each nanopore, that is, the width and depth, can be selected according to the needs of the application. The preferred size of the nanopore is: 10-100 nm in width and 4-50 μηι in depth. The number of nanopores can be adjusted according to the required output current value and voltage value. Preferably, the nanopores are uniformly distributed with a pore spacing of 2-30 μm, and more preferably have a uniform distribution of average pore spacing of 9 μm.

The working principle of the nano-friction generator shown in Figs. 14a and 14b will be specifically described below. When the layers of the nano-friction generator are bent downward, the surface of the second electrode 143 and the first polymer-polymer insulating layer 142 in the nano-friction generator rub against each other to generate an electrostatic charge, and the generation of the static charge causes the first electrode The capacitance between the 141 and the second electrode 143 is changed, resulting in a potential difference between the first electrode 141 and the second electrode 143. Since the first electrode 141 and the second electrode 143 are connected to the charging circuit module as the output electrode of the nano friction generator, and then connected to the super capacitor, the charging circuit module and the super capacitor constitute an external circuit of the nano friction generator, and the nano friction generator The two output electrodes are equivalent to being connected by an external circuit. When the layers of the nano-friction generator are restored to In the original state, the internal potential formed between the first electrode and the second electrode disappears at this time, and a reversed potential difference is again generated between the balanced first electrode and the second electrode. By repeated friction and recovery, periodic alternating current signals can be formed in the external circuit. The AC signal is processed by the charging circuit module and converted into a DC signal, which is output to the super capacitor for storage, thereby realizing self-charging of the super capacitor.

According to the research of the inventors, the metal rubs against the polymer, and the metal is more likely to lose electrons. Therefore, the friction between the metal electrode and the polymer can improve the energy output. Therefore, correspondingly, in the nano-friction generator shown in FIG. 14a and FIG. 14b, the second electrode is required to be rubbed as a friction electrode (ie, metal) with the first high-molecular polymer, so that the material thereof may be selected from metal or Alloy, wherein the metal may be gold, silver, platinum, palladium, aluminum, nickel, copper, titanium, chromium, selenium, iron, manganese, phase, tungsten or vanadium; the alloy may be an aluminum alloy, a titanium alloy, a magnesium alloy, a tantalum alloy , copper alloys, alloys, manganese alloys, nickel alloys, lead alloys, tin alloys, cadmium alloys, niobium alloys, indium alloys, gallium alloys, tungsten alloys, molybdenum alloys, milling alloys or niobium alloys. Since the first electrode does not need to be rubbed, in addition to the material of the second electrode listed above, other materials capable of fabricating the electrode may be applied, that is, the first electrode may be selected from a metal or an alloy. The metal may be gold, silver, platinum, palladium, aluminum, nickel, copper, titanium, chromium, selenium, iron, manganese, molybdenum, tungsten or vanadium; the alloy may be aluminum alloy, titanium alloy, magnesium alloy, niobium alloy, copper Alloy, alloy, manganese alloy, nickel alloy, lead alloy, tin alloy, cadmium alloy, niobium alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or niobium alloy, may also be selected from indium tin oxide Non-metallic materials such as graphene, silver nanowire film.

The second structure of the nano-friction generator is shown in Figures 15a and 15b. 15a and 15b are respectively a perspective structural view and a cross-sectional structural view showing a second structure of a nano-friction generator. The nano-friction generator includes: a first electrode 151, a first polymer insulating layer 152, a second polymer insulating layer 154, and a second electrode 153 which are sequentially stacked. Specifically, the first electrode 151 is disposed on the first side surface of the first polymer insulating layer 152; the second electrode 153 is disposed on the first side surface of the second polymer insulating layer 154; The second side surface of the high molecular polymer insulating layer 152 is in contact with the second side surface of the second polymer insulating layer 154 and induces electric charges at the first electrode 151 and the second electrode 153. Wherein, the first electrode 151 and the second electrode 153 constitute two output electrodes of the nano friction generator. In order to increase the power generation capability of the nano-friction generator, at least one of the two faces of the first polymer-polymer insulating layer 152 and the second polymer-polymer insulating layer 154 are provided with a micro-nano structure. In Fig. 15b, a micro-nano structure 155 is provided on the surface of the first polymer insulating layer 152. Therefore, when the nano-friction generator is squeezed, the opposing surfaces of the first polymer insulating layer 152 and the second polymer insulating layer 154 can better contact the friction, and at the first electrode 151 and the second More charge is induced at the electrode 153. The above micro-nano structure can be referred to the above description, and details are not described herein again.

The operation of the nano-friction generator shown in Figures 15a and 15b is similar to that of the nano-friction generator shown in Figures 14a and 14b. The only difference is that when the layers of the nano-friction generator shown in FIGS. 15a and 15b are bent, the surfaces of the first polymer-polymer insulating layer 152 and the second polymer-polymer insulating layer 154 are rubbed against each other to generate Static charge. Therefore, the working principle of the nano-friction generator shown in Figs. 15a and 15b will not be described here.

The nano-friction generator shown in Figs. 15a and 15b mainly generates an electric signal by friction between a polymer (first polymer polymer insulating layer) and a polymer (second polymer insulating layer).

In this structure, the material used for the first electrode and the second electrode may be indium tin oxide, graphene, silver nanowire film, metal or alloy, wherein the metal may be gold, silver, platinum, palladium, aluminum, nickel, Copper, titanium, chromium, selenium, iron, manganese, phase, tungsten or vanadium; alloys may be aluminum alloys, titanium alloys, magnesium alloys, niobium alloys, copper alloys, alloys, manganese alloys, nickel alloys, lead alloys, tin alloys , cadmium alloy, niobium alloy, indium alloy, gallium alloy, tungsten alloy, molybdenum alloy, niobium alloy or niobium alloy.

In the above two structures, the first polymer insulating layer and the second polymer insulating layer are respectively selected from the group consisting of polyimide film, aniline furfural resin film, polyacetal film, ethyl cellulose film, and poly Amide film, melamine furfural film, polyethylene glycol succinate film, cellulose film, cellulose acetate film, polyethylene adipate film, poly(phenylene terephthalate) film , cellulose sponge film, regenerated sponge film, polyurethane elastomer film, styrene propylene copolymer film, styrene butadiene copolymer film, rayon film, polyfluorene film, methacrylate film, polyvinyl alcohol film , polyvinyl alcohol film, polyester film, polyisobutylene film, polyurethane flexible sponge film, polyethylene terephthalate film, polyvinyl butyral film, furfural phenol film, neoprene film, D Diene propylene copolymer film, natural rubber film, polyacrylonitrile film, C One of a film of a nitrile vinyl chloride film and a polyethylene propylene glycol carbonate film. In principle, the materials of the first polymer insulating layer and the second polymer insulating layer may be the same or different. However, if the two layers of polymer insulation are made of the same material, the amount of charge that causes triboelectric charging is small. Therefore, it is preferable that the material of the first polymer insulating layer and the second polymer insulating layer are different.

In addition to the above two structures, the nano-friction generator can also be implemented with a third structure, as shown in Figures 16a and 16b. 16a and 16b are respectively a perspective structural view and a cross-sectional structural view showing a third structure of the nano-friction generator. As can be seen from the figure, the third structure adds an intervening film layer to the second structure, that is, the third structure of the nano-friction generator includes a first electrode 161 which is sequentially stacked, and the first high The molecular polymer insulating layer 162, the intermediate film layer 160, the second polymer insulating layer 164, and the second electrode 163. Specifically, the first electrode 161 is disposed on the first side surface of the first polymer insulating layer 162; the second electrode 163 is disposed on the first side surface of the second polymer insulating layer 164, and the intermediate film The layer 160 is disposed between the second side surface of the first polymer insulating layer 162 and the second side surface of the second polymer insulating layer 164. Wherein, at least one of the two faces opposite to each other of the intermediate film layer 160 and the first polymer insulating layer 162 is provided with a micro/nano structure 165, and/or the intermediate film layer 160 and the second high The micro-nano structure 165 is disposed on at least one of the two faces of the molecular polymer insulating layer 164. For the specific arrangement of the micro-nano structure 165, reference may be made to the above description, and details are not described herein again.

The material of the nano-friction generator shown in FIG. 16a and FIG. 16b can be selected by referring to the material of the nano-friction generator of the second structure described above. Wherein, the intermediate film layer may also be selected from the group consisting of transparent high-polymer polyethylene terephthalate (PET), polydisiloxane (PDMS), polystyrene (PS), and polyacrylonitrile. Any of ester (PMMA), polycarbonate (PC), and liquid crystal polymer (LCP). The material of the first polymer polymer insulating layer and the second polymer polymer insulating layer is preferably a transparent high polymer polyethylene terephthalate (PET); wherein, the intermediate film layer The material is preferably polydithiosiloxane (PDMS). The materials of the first polymer polymer insulating layer, the second polymer polymer insulating layer, and the intermediate film layer may be the same or different. However, if the material of the three-layer polymer insulating layer is the same, the amount of charge that causes triboelectric charging is small. Therefore, in order to improve the friction effect, the material of the intermediate film layer is different from that of the first polymer insulating layer and The second polymer polymer insulation layer, and the first polymer polymer The material of the edge layer and the second polymer insulating layer are preferably the same, so that the material type can be reduced and the production of the present invention can be made more convenient.

In the implementation shown in Figures 16a and 16b, the intervening film layer 160 is a layer of polymeric film, and thus substantially similar to the implementation shown in Figures 15a and 15b, still through the polymer (intermediate film layer) And the friction between the polymer (the second polymer insulation layer) to generate electricity. Among them, the intervening film layer is easy to prepare and has stable performance. In addition, the nano friction generator can also be implemented by using a fourth structure, as shown in FIG. 17a and FIG. 17b, including: a first electrode 171, a first polymer insulating layer 172, and an intervening electrode layer 170, which are sequentially stacked. a second polymer insulating layer 174 and a second electrode 173; wherein the first electrode 171 is disposed on the first side surface of the first polymer insulating layer 172; and the second electrode 173 is disposed on the second polymer On the first side surface of the polymer insulating layer 174, the intermediate electrode layer 170 is disposed between the second side surface of the first polymer insulating layer 172 and the second side surface of the second polymer insulating layer 174. The first polymer polymer insulating layer 172 is provided with a micro-nano structure on at least one of the surface of the inter-electrode layer 170 and the surface of the inter-electrode layer 170 opposite to the first polymer insulating layer 172 (not shown) The second polymer insulating layer 174 is provided with a micro/nano structure on at least one of the surface of the intermediate electrode layer 170 and the surface of the intermediate electrode layer 170 and the second polymer insulating layer 174 (not shown) ). In this manner, electrostatic charges are generated by friction between the inter-electrode electrode layer 170 and the first polymer-polymer insulating layer 172 and the second polymer-polymer insulating layer 174, thereby placing the intervening electrode layer 170 and the first electrode. A potential difference is generated between the 171 and the second electrode 173. At this time, the first electrode 171 and the second electrode 173 are connected in series as one output electrode of the nano-friction generator; the intermediate electrode layer 170 is the other output electrode of the nano-friction generator.

In the structure shown in FIG. 17a and FIG. 17b, the materials of the first polymer insulating layer, the second polymer insulating layer, the first electrode and the second electrode may refer to the nano friction of the second structure described above. The material of the generator is selected. The intervening electrode layer may be selected from a conductive film, a conductive polymer, a metal material, the metal material includes a pure metal and an alloy, and the pure metal is selected from the group consisting of gold, silver, platinum, palladium, aluminum, nickel, copper, titanium, chromium, selenium, iron, manganese. , phase, tungsten, vanadium, etc., the alloy may be selected from light alloys (aluminum alloy, titanium alloy, magnesium alloy, niobium alloy, etc.), heavy non-ferrous alloys (copper alloys, alloys, manganese alloys, nickel alloys, etc.), low melting point alloys (lead, tin, cadmium, antimony, indium, gallium and their alloys), refractory Alloys (tungsten alloys, molybdenum alloys, niobium alloys, tantalum alloys, etc.). The thickness of the intervening electrode layer 80 is preferably 100 μm to 500 μm, more preferably 200 μm.

The self-charging supercapacitor provided by the invention can realize self-charging function, and the self-charging supercapacitor can be arbitrarily bent and deformed by using flexible material, so that the self-charging supercapacitor of the invention can be adapted to different applications and environments. In addition, the present invention provides a high capacity retention rate and can achieve more efficient charge and discharge, and is an excellent energy storage device. In addition, the self-charging supercapacitor provided by the present invention has flexible, ingenious structure and better performance, and the shape and size can be processed according to the needs of the user, and is more convenient.

In the meantime, it is to be noted that the foregoing is only a specific embodiment of the present invention, and those skilled in the art can change and modify the present invention, and the modifications and variations are within the scope of the claims and the equivalents thereof. All should be considered as the scope of protection of the present invention.

Claims

Claim

A self-charging supercapacitor characterized by comprising:

a charging circuit module connected to an output electrode of the at least one nano-friction generator for regulating conversion of an electrical signal output by the nano-friction motor;

a supercapacitor connected to the charging circuit module for receiving an electrical signal output by the charging circuit module and storing the electrical signal.

2. The self-charging supercapacitor of claim 1 wherein said supercapacitor comprises:

Substrate

a separator on the substrate, a first electrode of the supercapacitor, a second electrode of the supercapacitor, and a first current collector and a second current collector;

Two bedding sheets on the first current collector and the second current collector, respectively;

An encapsulation layer that encapsulates the electrolyte;

3. The self-charging supercapacitor of claim 2, wherein the at least one nano-friction generator is disposed on one side of the ultracapacitor, and the at least one nano-friction generator is shared with the supercapacitor The substrate.

4. The self-charging supercapacitor according to claim 2, wherein the at least one nano-friction generator is disposed on both sides of the supercapacitor, and at least one nano-friction generating power disposed on a lower side of the supercapacitor And sharing the substrate with the supercapacitor An insulating layer is further disposed between the at least one nano-friction generator on the upper side of the supercapacitor and the supercapacitor.

5. The self-charging supercapacitor according to claim 1, wherein the supercapacitor comprises: a first current collector sequentially disposed in parallel, a supercapacitor first electrode, a separator, a supercapacitor second electrode, and a second a current collector; the charging circuit module is coupled to the first current collector and the second current collector.

6. The self-charging supercapacitor of claim 5, wherein the at least one nano-friction generator is disposed on one side of the ultracapacitor, the at least one nano-friction generator and the supercapacitor An insulating layer is also provided between them.

7. The self-charging supercapacitor according to claim 5, wherein the at least one nano-friction generator is disposed on both sides of the supercapacitor, and at least one nano-friction generating power disposed on a lower side of the supercapacitor A first insulating layer is further disposed between the machine and the supercapacitor, and a second insulating layer is disposed between the at least one nano-friction generator disposed on the upper side of the supercapacitor and the supercapacitor.

The self-charging supercapacitor according to claim 3 or 6, wherein the plurality of nano-friction generators are arranged in a plurality of layers, and the arrays are arranged in the same layer or in different layers to form a parallel structure.

The self-charging supercapacitor according to claim 4 or 7, wherein: there are a plurality of nano-friction generators disposed on a lower side of the supercapacitor, and the array is arranged in the same layer or different layers to form a parallel structure. ;

And/or, there are a plurality of nano-friction generators disposed on the upper side of the supercapacitor, and the arrays are arranged in the same layer or different layers to form a parallel structure.

10. The self-charging supercapacitor according to claim 2 or 5, wherein the supercapacitor is an all-solid supercapacitor selected from the group consisting of an all solid state symmetrical graphene supercapacitor, an all solid state symmetrical activated carbon supercapacitor, One of solid-state activated carbon and metal oxide asymmetric supercapacitor, all-solid activated carbon and conductive polymer asymmetric supercapacitor, all-solid activated carbon and lithium ion battery hybrid asymmetric supercapacitor.

11. The self-charging supercapacitor according to claim 2, wherein the material of the substrate is selected from the group consisting of polyethylene terephthalate, silicon, and silicon dioxide.

The self-charging supercapacitor according to claim 2, wherein the material of the two cushion sheets is selected from the group consisting of sodium butadiene rubber, styrene butadiene rubber, nitrile rubber, butyl rubber, silicone rubber, and urethane rubber. One of isoprene rubber, butadiene rubber, fluororubber and acrylate rubber.

The self-charging supercapacitor according to claim 2 or 5, wherein the separator is made of self-oxidized graphite, polyvinyl alcohol-sulfuric acid system, polyvinyl alcohol-phosphoric acid system, 1-butyl, 3 - mercapto imidazolium bistrifluorofluorenyl syl- syl-imide-smoke silica system, polyaniline-1-ethyl, 3-nonyl imidazolium tetrafluoroborate-trimethylsilyl alcohol system, 1-butyl , 3-mercaptoimidazole tetrafluoroborate-silica gel system, decyl acrylate-ethylene carbonate-propylene carbonate-lithium perchlorate system, decyl acrylate-ethylene carbonate-propylene carbonate - sodium perchlorate system, polyoxyethylene-polyethylene glycol-trifluoroantimony lithium dilithate system, polydecyl methacrylate-ethylene carbonate-propylene carbonate-tetraethyl perchlorate in the system One.

The self-charging supercapacitor according to claim 2, wherein the encapsulating layer is made of aluminum plastic film, polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene- One of a styrene copolymer, a polydecyl methacrylate, a polyfurfural, a polycarbonate, and a polyamide film.

The self-charging supercapacitor according to claim 2 or 5, wherein the materials of the first current collector and the second current collector are selected from one of copper, silver, aluminum and nickel; The material of the capacitor first electrode and the supercapacitor second electrode is selected from the group consisting of graphene, activated carbon, carbon aerogel, carbon fiber, metal oxide, conductive polymer, and lithium ion battery electrode material.

The self-charging supercapacitor according to claim 2, wherein the first electrode of the supercapacitor and the second electrode of the supercapacitor are: a parallel structure, a multi-column parallel structure, an interdigitated structure, a serpentine structure, a spiral Shape structure, dendritic structure, spiral dendritic structure or fingerprint structure.

The self-charging supercapacitor according to any one of claims 1 to 7, wherein the charging circuit module comprises:

And a filter circuit module connected to the rectifier circuit module for filtering a unidirectional pulse direct current outputted by the rectifier circuit module to obtain a direct current signal, wherein the filter circuit module outputs the direct current signal to the super capacitor.

The self-charging supercapacitor according to claim 17, wherein the charging circuit module further comprises: a charging control module and a switch/transformer module;

The charging control module is connected to the filter circuit module, and receives a DC signal output by the filter circuit module; the charging control module is connected to the super capacitor, and receives a charging voltage fed back by the super capacitor; the charging control module and The switch/transformer module is connected, and the charging control module obtains a control signal according to the direct current signal and the charging voltage, and outputs the control signal to the switch/transformer module;

The self-charging supercapacitor according to claim 18, wherein the charging circuit module further comprises: a generator control module;

The generator control module is coupled to the ultracapacitor and receives a charging voltage fed back by the supercapacitor;

The generator control module is coupled to the nano friction generator, and the generator control module outputs a signal to stop power generation to the nano friction generator according to the charging voltage.

The self-charging supercapacitor according to any one of claims 1 to 7, wherein the nano-friction generator comprises: a first electrode sequentially stacked, a first polymer insulating layer, and a first a second electrode; wherein the first electrode is disposed on a first side surface of the first polymer insulating layer; and a second side surface of the first polymer insulating layer faces the second The electrode is disposed, and the first electrode and the second electrode constitute an output electrode of the nano friction generator.

The self-charging supercapacitor according to claim 20, wherein the first polymer polymer insulating layer is provided with a micro/nano structure on a surface facing the second electrode.

The self-charging supercapacitor according to claim 20, wherein the nano-friction generator further comprises: a second portion disposed between the second electrode and the first polymer insulating layer a polymer electrolyte layer, the second electrode is disposed on the second polymer a first side surface of the polymer insulating layer; and a second side surface of the second polymer insulating layer is disposed opposite to the second side surface of the first polymer insulating layer.

The self-charging supercapacitor according to claim 22, wherein at least one of the two faces of the first polymer insulating layer and the second polymer insulating layer are oppositely disposed There is a micro-nano structure.

The self-charging supercapacitor according to claim 22, wherein the nano-friction generator further comprises: the first polymer insulating layer and the second polymer insulating layer An intervening film layer, wherein the intervening film layer is a polymer film layer, and the first polymer polymer insulating layer is opposite to the first polymer layer with respect to the surface of the intervening film layer and the intervening film layer At least one of the faces of the insulating layer and/or at least one of the surface of the second polymer insulating layer with respect to the intermediate film layer and the face of the intermediate film layer with respect to the second polymer insulating layer A micro-nano structure is provided on one side.

The self-charging supercapacitor according to any one of claims 1 to 7, wherein the nano-friction generator comprises: a first electrode sequentially stacked, a first polymer insulating layer, and an intermediate electrode a second polymer sealing layer and a second electrode; wherein the first electrode is disposed on a first side surface of the first polymer insulating layer; On the first side surface of the second polymer insulating layer, the intervening electrode layer is disposed on the second side surface of the first polymer insulating layer and the second polymer insulating layer Between the two side surfaces, and the surface of the first polymer insulating layer opposite to the intermediate electrode layer and the surface of the intervening electrode layer relative to the first polymer polymer insulating layer and/or The second polymer insulating layer is provided with a micro/nano structure on at least one of a surface of the intervening electrode layer and a surface of the interposing electrode layer and the second polymer insulating layer, An electrode and a second electrode are connected to form an output electrode of the nano friction generator with the intervening electrode layer.