CN106887969B - Self-charging system based on flexible electric spinning reticular membrane and wearable electronic - Google Patents
Self-charging system based on flexible electric spinning reticular membrane and wearable electronic Download PDFInfo
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- CN106887969B CN106887969B CN201710153556.8A CN201710153556A CN106887969B CN 106887969 B CN106887969 B CN 106887969B CN 201710153556 A CN201710153556 A CN 201710153556A CN 106887969 B CN106887969 B CN 106887969B
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/04—Friction generators
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/32—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries for charging batteries from a charging set comprising a non-electric prime mover rotating at constant speed
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
- H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
- H02J7/34—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering
- H02J7/345—Parallel operation in networks using both storage and other dc sources, e.g. providing buffering using capacitors as storage or buffering devices
-
- 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
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B40/00—Technologies aiming at improving the efficiency of home appliances, e.g. induction cooking or efficient technologies for refrigerators, freezers or dish washers
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Power Engineering (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention provides a kind of preparation methods of flexible electric spinning reticular membrane, include the following steps：The non-conductive polymer of predetermined amount is distributed in solvent, to obtain the polymer solution that mass concentration is 8 15%；Polymer solution is added in the container with jet port, is 0.6 1.2mL/h using syringe pump control injection speed, and adds the voltage of 12 18kV between jet port and ground connection receiving terminal, to form fibrous web-like film in ground connection receiving terminal；Fibrous web-like film is subjected to pre-oxidation treatment in air atmosphere, to obtain the netted film of polymer fiber；High temperature cabonization processing is carried out in an inert atmosphere with by the netted film of polymer fiber, to obtain carbon fiber reticular membrane.These constituents for being prepared using the method for the present invention are impure less, it is pollution-free to stablize, and are preparing flexible friction nano generator, flexible solid-state supercapacitor and assembling post-processing step of the process of self-charging system without any template and complexity.
Description
Technical field
The present invention relates to nano generators and ultracapacitor field, more particularly to a kind of flexible electric spinning reticular membrane
Preparation method, based on the flexible friction nano generator of the flexible electric spinning reticular membrane, flexible solid-state supercapacitor, self-charging
System and wearable electronic.
Background technology
Friction nanometer power generator has many advantages, such as at low cost, high efficiency, pollution-free.The output of friction nanometer power generator is peak
Value, exchange output, therefore, it cannot directly drive electronic equipment.And most of electricity consumption situation, which is not power generation, directly to be made
With, but need to be stored and reuse.So can shape be combined with apparatus for storing electrical energy for friction nanometer power generator
Forming is same, to be stablized and lasting output.Storage electrical energy system more ripe at present has lithium ion battery and super electricity
Container.Compared to lithium ion battery, the advantage of ultracapacitor is high-energy density, long circulating density and environmental-friendly
Deng.Therefore, for for collecting friction nanometer power generator in the pulse electric energy of low frequency institute output, ultracapacitor is preferably to select
It selects.Friction nanometer power generator is combined with ultracapacitor, to which composition can convert mechanical energy to what electric energy can simultaneously store
Self-charging system.
Usual most easy friction nanometer power generator includes two kinds of materials：When the electrode of friction nanometer power generator, simultaneously
It can be used as the preferable frictional layer of electric conductivity；Second is that the friction material that electric conductivity is poor.Most easy ultracapacitor is parallel-plate
Solid-state super capacitor comprising there is the active material of diaphragm and capacitive properties also to can be used as electrode.Electric conductivity is poor to rub
Wipe layer, usually polymer, such as PTFE, PP；Electrode material is usually metal, such as copper, aluminium, titanium sheet, these metals are one
It is easily oxidized and corrodes under conditions of fixed.In the recent period, consider from cost, stability etc., non-metal electrode is more
Researcher concern.Wherein non-metal electrode is roughly divided into two classes：When conducting polymer, such as polypyrrole；Second is that carbon material,
Such as graphene, carbon pipe.The method for preparing polypyrrole using electrodeposition process exists in the prior art, but electrochemical deposition method is wanted
It asks and is necessary for metallic conduction substrate, and electrochemical appliance is needed to configure during industrial practice, be unfavorable for mass producing, at
This height, poor repeatability.Simultaneously in the work using polypyrrole as the friction nanometer power generator and ultracapacitor of electrode and frictional layer
It is formed by self-charging system inflexibility, this has limited to the application range of the system collecting mechanical energy.
Therefore, work out a kind of simple, easy to operate, at low cost, pollution-free, the efficient flexible self-charging system of component with
Meeting application demand has great significance.
Invention content
It is an object of the present invention to overcome the structure band of existing friction nanometer power generator and solid-state super capacitor
The disadvantage come, provides a kind of preparation method of flexible electric spinning reticular membrane, and the flexible electric spinning reticular membrane application that will be prepared
In friction nanometer power generator and the structure of solid-state super capacitor, and thus assembling is obtained based on flexible electric spinning reticular membrane
Self-charging system.
A further object of the present invention is to meet the power demands now for portable wearable electronic.For
Meet the needs of society now, such as flexible integration as wearable display, electronic skin and distributing sensor
Portable wearable device is fast-developing.So the power supply of these equipment also needs to meet flexible, wearable, light etc. want
It asks.And the present invention is the self-charging system based on flexible electric spinning reticular membrane, can be applied to drive a series of portable electronics
Equipment.Friction nanometer power generator in the system can collect mechanical energy caused by human motion, and be translated into electric energy.
This part electric energy can be stored in solid-state super capacitor through over commutation, so that solid-state super capacitor can drive electricity
Sub- equipment.
Particularly, the present invention provides a kind of preparation method of flexible electric spinning reticular membrane, include the following steps：
The non-conductive polymer of predetermined amount is distributed in solvent, it is molten for the polymer of 8-15% to obtain mass concentration
Liquid；
The polymer solution is added in the container with jet port, is 0.6- using syringe pump control injection speed
1.2mL/h, and jet port and ground connection receiving terminal between plus 12-18kV voltage so that the polymer solution is in voltage
It sprays and is stretched from the jet port under electrostatic interaction, and cure along with the volatilization of the solvent, to be connect described
Ground receiving terminal forms fibrous web-like film；
The fibrous web-like film is subjected to pre-oxidation treatment in air atmosphere, to obtain the netted film of polymer fiber；With
The netted film of the polymer fiber is subjected to high temperature cabonization processing in an inert atmosphere, it is netted to obtain carbon fiber
Film.
Further, the distance between the jet port and the ground connection receiving terminal are 10-20cm；
Wherein, the treatment temperature that the fibrous web-like film carries out pre-oxidation treatment in air atmosphere is 200-280 DEG C；
Wherein, the treatment temperature that the netted film of the polymer fiber carries out high temperature cabonization processing in an inert atmosphere is 600-
900℃。
Further, the non-conductive polymer be selected from polyacrylonitrile, polyethylene pyrrole network alkanone, polymethacrylates,
It is polymethyl methacrylate, makrolon, polyimides, polyethylene terephthalate, polyamide, polyvinyl alcohol, poly- different
One or more combinations in butylene, poly bis phenol carbonate and polyvinyl chloride.
Particularly, the present invention provides a kind of flexible friction nano generators based on flexible electric spinning reticular membrane, including：
The netted film layer of first carbon fiber, the carbon fiber reticular membrane obtained by above-mentioned preparation method are formed；
First polymer fibrous web-like film layer, the netted film of polymer fiber obtained by above-mentioned preparation method are formed,
The lower surface of the upper surface of the first polymer fibrous web-like film layer and the netted film layer of the first carbon fiber be oppositely arranged or
The lower surface of first polymer fibrous web-like film layer described in person and the upper surface of the netted film layer of the first carbon fiber are oppositely arranged；
With
It is formed in the upper surface of the first polymer fibrous web-like film layer or the conductive layer of lower surface；
Wherein, the netted film layer of first carbon fiber and the first polymer fibrous web-like layer structure are rubbed at described
Nano generator is wiped by can occur relative displacement when outer force effect, and by the netted film layer of first carbon fiber and described is led
The outside circuit output electric signal of electric layer.
Further, the netted film layer of the first carbon fiber causes the first arch shape, the first polymer fibrous web-like
Layer structure is at the second arch shape corresponding with first arch shape of the netted film layer of the first carbon fiber；
Wherein, when the friction nanometer power generator is by outer force effect, the netted film layer of first carbon fiber and described
First polymer fibrous web-like film layer can become stretched condition from flexuosity so that the netted film layer of the first carbon fiber and
Relative displacement occurs between the first polymer fibrous web-like film layer, to export electric signal；
In the release of the external force that the friction nanometer power generator is subject to, the netted film layer of first carbon fiber and described
First polymer fibrous web-like film layer can become flexuosity from stretched condition so that the netted film layer of the first carbon fiber and
Relative displacement occurs between the first polymer fibrous web-like film layer, to export opposite electric signal.
Particularly, the present invention provides a kind of flexible solid-state supercapacitors based on flexible electric spinning reticular membrane, including：
Second polymer fibrous web-like film layer, the netted film of polymer fiber obtained by above-mentioned preparation method are formed；
With
It is formed in two layers of netted film layers of second carbon fiber of the second polymer fibrous web-like film layer both sides, each carbon fiber
The carbon fiber reticular membrane that netted film layer is obtained by above-mentioned preparation method is tieed up to be formed.
Further, phase between the second polymer fibrous web-like film layer and the netted film layer of two layers of second carbon fibers
Mutually it is arranged in parallel.
Particularly, the present invention provides a kind of self-charging systems based on flexible electric spinning reticular membrane, wherein including：
Above-mentioned flexible friction nano generator；
Above-mentioned flexible solid-state supercapacitor；With
Rectifier bridge, the ac signal for exporting the flexible friction nano generator are converted into DC signal,
And the DC signal is exported to the flexible solid-state supercapacitor.
Wherein, the quantity of the flexible friction nano generator and the flexible solid-state supercapacitor is at least one respectively
It is a.
Further, multiple flexible friction nano generators are in parallel, multiple flexible solid-state supercapacitor strings
Connection；
Wherein, concatenated flexibility is determined according to the electric signal of the multiple flexible friction nano generator output after parallel connection
The quantity of solid-state super capacitor, so that the electric signal of flexible solid-state supercapacitor input is received with the flexible friction
The electric signal of rice generator output matches.
Particularly, described to wear the present invention provides a kind of wearable electronic based on flexible electric spinning reticular membrane
Wearing electronic equipment obtains electricity from above-mentioned self-charging system.
The solution of the present invention can utilize the preparation method of flexible electric spinning reticular membrane to prepare flexible friction nanometer generating
The constituent of machine, flexible solid-state supercapacitor and self-charging system, including the netted film of polymer fiber and carbon fiber it is netted
Film.These constituents for being prepared using this method are impure less, it is pollution-free to stablize, and are preparing flexible friction nanometer generating
Post-processing step of the process of machine, flexible solid-state supercapacitor and assembling self-charging system without any template and complexity.
The flexible friction nano generator of the present invention can be used for collecting various mechanical energy, and convert the mechanical energy to electricity
Energy.The working condition of the flexible friction nano generator is flexible and stretches, and flexible characteristic has expanded application field, can be used as
The component part of self-charging system, and a variety of portable wearable electronics are driven by the self-charging system, meet day increasingly
The social demand of exhibition.
In addition, the flexible electric spinning reticular membrane of the present invention is not high to equipment requirement from the process for being prepared into application, it is at low cost.
Friction nanometer power generator and solid-state super capacitor working mechanism are simple, and the course of work is without danger, efficient, industrialization promotion
By force, there is significant economic benefit and social benefit.
According to the following detailed description of specific embodiments of the present invention in conjunction with the accompanying drawings, those skilled in the art will be brighter
The above and other objects, advantages and features of the present invention.
Description of the drawings
Some specific embodiments that the invention will be described in detail by way of example and not limitation with reference to the accompanying drawings hereinafter.
Identical reference numeral denotes same or similar component or part in attached drawing.It should be appreciated by those skilled in the art that these
What attached drawing was not necessarily drawn to scale.In attached drawing：
Fig. 1 is the preparation method of polymer fiber according to an embodiment of the invention netted film and carbon fiber reticular membrane
Flow diagram；
Fig. 2 is that the preparation process of the netted film of polymer fiber according to an embodiment of the invention and carbon fiber reticular membrane is shown
It is intended to；
Fig. 3 is the scanning electron microscope diagram of fibrous web-like film according to an embodiment of the invention；
Fig. 4 is the scanning electron microscope diagram of the netted film of polymer fiber according to an embodiment of the invention；
Fig. 5 is the scanning electron microscope diagram of carbon fiber reticular membrane according to an embodiment of the invention；
Fig. 6 is the flexible friction nano generator according to an embodiment of the invention based on flexible electric spinning reticular membrane
Structural schematic diagram；
Fig. 7 is being opened under different motion frequency for single flexible friction nanometer power generator according to an embodiment of the invention
The output figure of road voltage, short circuit current and short-circuit electricity；
Fig. 8 is the flexible solid-state supercapacitor according to an embodiment of the invention based on flexible electric spinning reticular membrane
Structural schematic diagram；
Fig. 9 is cycle volt of the single solid-state super capacitor according to an embodiment of the invention under different scanning rates
Pacify curve；
Figure 10 is that the structure of the self-charging system according to an embodiment of the invention based on flexible electric spinning reticular membrane is shown
It is intended to；
Figure 11 is that three friction nanometer power generators according to an embodiment of the invention are in parallel whole in different motion frequency
Electric current output after lower rectification；
Figure 12 is that three solid-state super capacitors series connection according to an embodiment of the invention is whole under different electric currents
Constant current charge-discharge curve；
Figure 13 is that self-charging system according to an embodiment of the invention collects mechanical energy under 5Hz frequencies and what is stored fill
Electric curve, and the discharge curve using the system drive electronic watch.
Specific implementation mode
Fig. 1 and Fig. 2 respectively illustrates the stream of the preparation method of the netted film 120 of polymer fiber and carbon fiber reticular membrane 130
Journey schematic diagram and preparation process schematic diagram.As depicted in figs. 1 and 2, the preparation method of flexible electric spinning reticular membrane of the invention, packet
Include following steps：
S100, the non-conductive polymer of predetermined amount is distributed in solvent, to obtain mass concentration as the polymerization of 8-15%
Object solution；
S200, the polymer solution is added in the container with jet port, is using syringe pump control injection speed
0.6-1.2mL/h, and jet port and ground connection receiving terminal between plus 12-18kV voltage so that the polymer solution is in electricity
It sprays and is stretched from the jet port under pressure electrostatic interaction, and cure along with the volatilization of the solvent, to be connect in the ground connection
Receiving end forms fibrous web-like film 110；
S300, the fibrous web-like film 110 is subjected to pre-oxidation treatment in air atmosphere, it is netted to obtain polymer fiber
Film 120；With
S400, the netted film of the polymer fiber 120 is subjected to high temperature cabonization processing in an inert atmosphere, to obtain carbon fiber
Reticular membrane 130.
In one embodiment, it is 1 that step S100, which is specially by mass ratio,:9 polyacrylonitrile (PAN) and dimethyl formyl
Amine (DMF) is mixed at normal temperatures, and stirs 12h, obtains uniformly mixed polymer solution.Step S200 is specially to utilize
5mL syringes draw a certain amount of polymer solution, No. 21 syringe needles of adapted, syringe needle, that is, jet port, and are disposed at syringe pump,
It is 0.8mL/h using syringe pump control injection speed, it is 10cm to adjust the distance between syringe needle and the ground connection receiving terminal of ground connection, and
Add the voltage of 15V at its both ends, wherein spinning injection solution is 2mL, so that the polymer solution is under voltage electrostatic interaction
It sprays and is stretched from syringe needle, and cure along with the volatilization of solvent, then collect to obtain fiber in ground connection receiving terminal, spin
After silk 2h, PAN fiber reticular membrane 110 is obtained in ground connection receiving terminal.Fig. 3 shows the PAN fiber reticular membrane of the embodiment of the present invention
110 scanning electron microscope diagram.It can be seen from Fig. 3 that the diameter of PAN fiber reticular membrane 110 is about 200nm.In order to enable PAN
Fibrous web-like film 110 is in stable state, and step S300 is specially that PAN fiber reticular membrane 110 is placed in Muffle furnace to carry out in advance
Oxidation processes, controlled at 240 DEG C, processing time 2h, to obtain the netted film of polymer fiber 120.Fig. 4 shows this hair
The scanning electron microscope diagram of the netted film of the polymer fiber of bright embodiment 120.In order to enhance the netted film of polymer fiber 120
Electric conductivity, step S400 is specially that the netted film of polymer fiber that step S300 is obtained 120 is placed in tube furnace, and in argon gas
Carbonization treatment is carried out under atmosphere, control heating rate is 5 DEG C/min, is warming up to 800 DEG C, obtains carbon fiber reticular membrane 130.Fig. 5
Show the scanning electron microscope diagram of the carbon fiber reticular membrane 130 of the embodiment of the present invention.
In another embodiment, with above-described embodiment difference lies in, in step S100 by mass ratio be 1:8 polyethylene
Pyrrole network alkanone (PVP) and dimethylformamide (DMF) are mixed at normal temperatures, and stir 13h, obtain uniformly mixed polymerization
Object solution.Be 1mL/h using syringe pump control injection speed in step S200, adjust syringe needle and ground connection ground connection receiving terminal it
Between distance be 15cm, and add the voltage of 18V at its both ends, PVP fibrous web-likes film 110 obtained in ground connection receiving terminal.Step
In S300, controlled at 200 DEG C, processing time 3h, to obtain the netted film of polymer fiber 120.In step S400, control
Heating rate is 3 DEG C/min, is warming up to 600 DEG C, obtains carbon fiber reticular membrane 130.In other embodiments, in step S100,
Polymer can be selected from polymethacrylates, polymethyl methacrylate, makrolon, polyimides, poly terephthalic acid
One or more groups in glycol ester, polyamide, polyvinyl alcohol, polyisobutene, poly bis phenol carbonate and polyvinyl chloride
It closes.In step S200, it is any speed in 0.6-1.2mL/h using syringe pump control injection speed, adjusts syringe needle and ground connection
Ground connection the distance between receiving terminal be any value in 10-20cm, and any voltage in its both ends adds 12-18V is connecing
Ground receiving terminal obtains fibrous web-like film 110.In step S300, controlled at any temperature in 200-280 DEG C, processing time is
1-5h, to obtain the netted film of polymer fiber 120.In step S400, control heating rate is 1-10 DEG C/min, is warming up to 600-
Any temperature in 900 DEG C obtains carbon fiber reticular membrane 130.
Netted 120 electric conductivity of film of polymer fiber being prepared according to the method described above is poor, the carbon fiber being prepared
Reticular membrane 130 has good electric conductivity.These constituents for being prepared using this method are impure less and to be stablized pollution-free.
In addition, the preparation process of flexible electric spinning reticular membrane is not high and at low cost to equipment requirement, can mass produce.
Fig. 6 shows the flexible friction nanometer generating according to an embodiment of the invention based on flexible electric spinning reticular membrane
The structural schematic diagram of machine 200.200 generality of flexible friction nano generator based on flexible electric spinning reticular membrane of the present invention can
To include two layers of frictional layer and two conductive layers 230, wherein opposite position can occur under external forces for two layers of frictional layer
It moves, and passes through the 230 outside circuit output electric signal of two conductive layers.It will be prepared using above-mentioned preparation method in the present invention
The netted film 120 of polymer fiber and carbon fiber reticular membrane 130 are applied to friction nanometer power generator.Due to carbon fiber reticular membrane 130
With good electric conductivity, and the electric conductivity of the netted film of polymer fiber 120 is poor.Therefore, as shown in fig. 6, the present invention's is soft
Frottage nano generator 200 includes three-decker, is the netted film layer 210 of the first carbon fiber, first polymer web respectively
Shape film layer 220 and conductive layer 230.Wherein, the netted film layer of the first carbon fiber 210 is not only used as frictional layer, but also as conductive layer 230.
First polymer fibrous web-like film layer 220 is used as another frictional layer.The specific configuration of the three-decker and mutual connection
Relationship is：The lower surface phase of the netted film layer of the upper surface of the first polymer fibrous web-like film layer 220 and first carbon fiber 210
To the upper table of the netted film layer of lower surface and first carbon fiber of setting or the first polymer fibrous web-like film layer 220 210
Face is oppositely arranged.The conductive layer 230 is formed in the upper surface or lower surface of the first polymer fibrous web-like film layer 220.Its
In, the netted film layer 210 of first carbon fiber and the first polymer fibrous web-like film layer 220 are configured in the friction nanometer generating
Machine is and outside by the netted film layer 210 of first carbon fiber and the conductive layer 230 by can occur relative displacement when outer force effect
Circuit output electric signal.
In the embodiment shown in fig. 6, the netted film layer of first carbon fiber 210 causes the first arch shape, first polymerization
The netted film layer of fibres 220 is configured to second arch corresponding with the first arch shape of the netted film layer of first carbon fiber 210
Shape.Wherein, when the friction nanometer power generator is by outer force effect, the netted film layer 210 of first carbon fiber and first polymerization
The netted film layer 220 of fibres can become stretched condition from flexuosity so that the netted film layer 210 of first carbon fiber and this
Relative displacement occurs between the netted film layer of one polymer fiber 220, to export electric signal.It is subject in the friction nanometer power generator
When the external force discharges, the netted film layer 210 of first carbon fiber and the first polymer fibrous web-like film layer 220 can be from stretched conditions
Become flexuosity, so that being sent out between the netted film layer 210 of first carbon fiber and the first polymer fibrous web-like film layer 220
Raw relative displacement, to export opposite electric signal.Wherein, electrode is attached at the surface of 120 layers of polymeric web shape film, and with
The construction of 120 layers of the netted film of the polymer fiber is consistent substantially.In this embodiment it is possible to by another first carbon fibre web
Shape film layer 210 is used as electrode layer.
The area of electric signal and frictional layer that flexible friction nano generator 200 exports has certain relationship.Fig. 7 is shown
Open-circuit voltage, the short circuit electricity under different motion frequency of the single flexible friction nanometer power generator 200 of one embodiment of the invention
The output figure of stream and short-circuit electricity.In the embodiment shown in fig. 7, the frictional layer area of flexible friction nano generator 200
For 2 × 2cm, the output valve of open-circuit voltage, short circuit current and short-circuit electricity is as shown in Figure 7 under different motion frequency.By Fig. 7
In it is found that the open-circuit voltage output of single friction nanometer power generator is maintained at 91V at different frequencies；Its short circuit current exported
Increase with the increase of frequency, when frequency is 2Hz, the peak value of short circuit current is 2 μ A, when frequency increases to 8Hz, short circuit
The peak value of electric current can reach 4.8 μ A；The short-circuit electricity that it is exported is also almost unchanged at different frequencies, is maintained at the left sides 26nC
It is right.
Fig. 8 shows the flexible solid super capacitor according to an embodiment of the invention based on flexible electric spinning reticular membrane
The structural schematic diagram of device 300.The flexible solid-state supercapacitor 300 based on flexible electric spinning reticular membrane of the present invention it is general every
Two layers of active material layer and two layers of electrode layer being separately positioned on the outside of two layers of active material layer in diaphragm both sides is arranged in film.
The netted film 120 of the polymer fiber prepared using above-mentioned preparation method and carbon fiber reticular membrane 130 are applied in the present invention
Flexible solid-state supercapacitor 300.Since carbon fiber reticular membrane 130 has good electric conductivity, and the netted film of polymer fiber
120 electric conductivity is poor.Therefore, as shown in figure 8, the flexible solid-state supercapacitor 300 of the present invention includes three-decker, second
The netted film layer 310 of polymer fiber and two layers of second carbon fibers for being formed in 310 both sides of second polymer fibrous web-like film layer
Netted film layer 320.Wherein, the netted film layer 320 of wherein one layer of second carbon fiber in the netted film layer of two layers of second carbon fibers 320 is made
For active material layer and the corresponding electrode layer in 310 the same side of second polymer fibrous web-like film layer is arranged.Another layer second
The netted film layer of carbon fiber 320 is as being arranged in the active material layer of 310 other side of second polymer fibrous web-like film layer and corresponding
Electrode layer.The three-decker is arranged in parallel, forms parallel-plate solid-state super capacitor.
Fig. 9 shows single solid-state super capacitor following under different scanning rates according to an embodiment of the invention
Ring volt-ampere curve.In the embodiment shown in fig. 9, solid-state electrolytic solution used by the solid-state super capacitor is solidifying for KOH/PVA
Glue (5g KOH and 5g PVA are dissolved in 50mL water), diaphragm are the netted film 120 of polymer fiber, and electrode and active material are all carbon fiber
Tie up reticular membrane 130, wherein the quality of active material determines the capacitance of ultracapacitor, and therefore, monopole is lived in the present embodiment
Property substance quality be 0.1mg.The results are shown in Figure 9 for the output of single solid-state super capacitor.As seen from Figure 9, for
Under conditions of sweeping speed more slowly, cyclic voltammetry curve is shown the cyclic voltammetry curve of the solid-state super capacitor close to rectangle
Good capacitance characteristic.With the increase for sweeping speed, cyclic voltammetry curve is gradually deviated from rectangle, shows larger resistance characteristic.
Figure 10 shows the self-charging system 400 according to an embodiment of the invention based on flexible electric spinning reticular membrane
Structural schematic diagram.400 generality of self-charging system may include above-mentioned flexible friction nano generator 200, above-mentioned soft
Property solid-state super capacitor 300 and the rectifier bridge for connecting the two.The self-charging system 400 is from being prepared into application, it is only necessary to
It is completed according to following three steps.Step 1: preparing the netted film 120 of polymer fiber and carbon fibre web using electrical spinning method
Shape film 130.Step 2: being formed using the netted film 120 of polymer fiber and the assembling of carbon fiber reticular membrane 130 of step 1 acquisition soft
Frottage nano generator 200 and flexible solid-state supercapacitor 300, and test its electricity output.Step 3: according to individual devices
Performance output, by series-parallel circuit management the output of two kinds of devices is mutually matched, to realize self-charging system 400
Assembling.Wherein, part has been discussed in detail in front for step 1 and step 2, and details are not described herein again.
In above-mentioned steps three, by the test of step 2, two kinds of devices are assembled into the self-charging system that can be worked
400, it needs to carry out circuit design and management.In embodiments of the present invention, according to friction nanometer power generator high voltage low current
Output characteristics, using three friction nanometer power generator parallel connections as the first part in system, subsequent rectifier bridge will exchange electricity output
Switch to direct current electricity output.Figure 11 shows the electric current output of three friction nanometer power generator parallel connections after rectification.As shown in Figure 11,
Its electric current still increases with the increase of motion frequency, and when frequency is 2Hz, electric current is 4.7 μ A, when frequency increases to 8Hz
When, electric current is 10.4 μ A.By three solid-state super capacitor series connection as the second part in system, in order to match friction nanometer
The output of generator, serial connected super capacitor can reduce whole capacity and can increase controllable voltage so that fill certainly
Electric system 400 is applicable to more electronic equipments.Figure 12 is three solid state super capacitors according to an embodiment of the invention
The whole constant current charge-discharge curve under different electric currents of device series connection.As shown in Figure 12, when input current is 5 μ A, three solid-states
Capacity after ultracapacitor series connection is 1.37mF.After the assembling for completing self-charging system 400, in the present embodiment, in 5Hz
Motion frequency under test self-charging system 400 of the present invention.Figure 13 show self-charging system 400 charging curve and
Utilize the discharge curve of the system drive portable electric sublist.
Due to the self-charging system 400 being made of flexible friction nano generator 200 and flexible solid-state supercapacitor 300
To be flexible, therefore, the self-charging system 400 in the present invention can be applied to such as wearable display, electronic skin and divide
It dissipates in the portable wearable device of flexible integration as formula sensor, to drive these portable wearable devices.
The solution of the present invention can utilize the preparation method of flexible electric spinning reticular membrane to prepare flexible friction nanometer generating
The constituent of machine 200, flexible solid-state supercapacitor 300 and self-charging system 400, including the netted film of polymer fiber 120
With carbon fiber reticular membrane 130.These constituents for being prepared using this method are impure less, it is pollution-free to stablize, and are preparing
The process of flexible friction nano generator 200, flexible solid-state supercapacitor 300 and assembling self-charging system 400 is without any
Template and complicated post-processing step.
The flexible friction nano generator 200 of the present invention can be used for collecting various mechanical energy, and convert the mechanical energy to
Electric energy.The working condition of the flexible friction nano generator 200 is flexible and stretches, and flexible characteristic has expanded application field,
The component part of self-charging system 400 is can be used as, and drives a variety of portable wearable electronics to set by the self-charging system 400
It is standby, meet growing social demand.
In addition, the flexible electric spinning reticular membrane of the present invention is not high to equipment requirement from the process for being prepared into application, it is at low cost.
Friction nanometer power generator and solid-state super capacitor working mechanism are simple, and the course of work is without danger, efficient, industrialization promotion
By force, there is significant economic benefit and social benefit.
So far, although those skilled in the art will appreciate that present invention has been shown and described in detail herein multiple shows
Example property embodiment still without departing from the spirit and scope of the present invention, still can according to the present disclosure directly
Determine or derive many other variations or modifications consistent with the principles of the invention.Therefore, the scope of the present invention is understood that and recognizes
It is set to and covers other all these variations or modifications.
Claims (8)
1. a kind of flexible friction nano generator based on flexible electric spinning reticular membrane, wherein including：
The netted film layer of first carbon fiber, is formed by carbon fiber reticular membrane；
First polymer fibrous web-like film layer is formed by the netted film of polymer fiber, the first polymer fibrous web-like film
The upper surface of layer is oppositely arranged with the lower surface of the netted film layer of the first carbon fiber or the first polymer fibrous web-like
The lower surface of film layer and the upper surface of the netted film layer of the first carbon fiber are oppositely arranged；With
It is formed in the upper surface of the first polymer fibrous web-like film layer or the conductive layer of lower surface；
Wherein, the netted film layer of first carbon fiber and the first polymer fibrous web-like layer structure are received in the friction
Rice generator is passed through the netted film layer of first carbon fiber and the conductive layer by relative displacement can occur when outer force effect
Outside circuit output electric signal；
The first carbon fiber reticular membrane and the netted film of the polymer fiber are made by following preparation methods：
The non-conductive polymer of predetermined amount is distributed in solvent, to obtain mass concentration as the polymer solution of 8-15%；
The polymer solution is added in the container with jet port, is 0.6- using syringe pump control injection speed
1.2mL/h, and jet port and ground connection receiving terminal between plus 12-18kV voltage so that the polymer solution is in voltage
It sprays and is stretched from the jet port under electrostatic interaction, and cure along with the volatilization of the solvent, to be connect described
Ground receiving terminal forms fibrous web-like film；
The fibrous web-like film is subjected to pre-oxidation treatment in air atmosphere, to obtain the netted film of polymer fiber；With
The netted film of the polymer fiber is subjected to high temperature cabonization processing in an inert atmosphere, to obtain carbon fiber reticular membrane.
2. flexible friction nano generator according to claim 1, wherein the netted film layer of the first carbon fiber causes
One arch shape, the first polymer fibrous web-like layer structure is at the first arch shape with the netted film layer of the first carbon fiber
Corresponding second arch shape；
Wherein, when the friction nanometer power generator is by outer force effect, the netted film layer of first carbon fiber and described first
The netted film layer of polymer fiber can become stretched condition from flexuosity, so that the netted film layer of first carbon fiber and described
Relative displacement occurs between first polymer fibrous web-like film layer, to export electric signal；
In the release of the external force that the friction nanometer power generator is subject to, the netted film layer of first carbon fiber and described first
The netted film layer of polymer fiber can become flexuosity from stretched condition, so that the netted film layer of first carbon fiber and described
Relative displacement occurs between first polymer fibrous web-like film layer, to export opposite electric signal.
3. flexible friction nano generator according to claim 1, wherein the jet port and the ground connection receiving terminal it
Between distance be 10-20cm；
Wherein, the treatment temperature that the fibrous web-like film carries out pre-oxidation treatment in air atmosphere is 200-280 DEG C；
Wherein, the treatment temperature that the netted film of the polymer fiber carries out high temperature cabonization processing in an inert atmosphere is 600-900
℃。
4. flexible friction nano generator according to claim 3, wherein the non-conductive polymer is selected from polypropylene
Nitrile, polymethacrylates, polymethyl methacrylate, makrolon, polyimides, gathers to benzene two at polyethylene pyrrole network alkanone
It is one or more in formic acid glycol ester, polyamide, polyvinyl alcohol, polyisobutene, poly bis phenol carbonate and polyvinyl chloride
Combination.
5. a kind of self-charging system based on flexible electric spinning reticular membrane, wherein including：
Flexible friction nano generator according to any one of claims 1-4；
Flexible solid-state supercapacitor, the flexible solid-state supercapacitor include：Second polymer fibrous web-like film layer, by
The netted film of the polymer fiber for forming the first polymer fibrous web-like film layer of the flexible friction nano generator is formed；
With two layers of netted film layers of second carbon fiber for being formed in the second polymer fibrous web-like film layer both sides, each carbon fiber is netted
Film layer is formed by the carbon fiber reticular membrane for forming the netted film layer of the first carbon fiber of the flexible friction nano generator；With
Rectifier bridge, the ac signal for exporting the flexible friction nano generator are converted into DC signal, and will
The DC signal is exported to the flexible solid-state supercapacitor；
Wherein, the quantity of the flexible friction nano generator and the flexible solid-state supercapacitor is at least one respectively.
6. self-charging system according to claim 5, wherein multiple flexible friction nano generators are in parallel, multiple
The flexible solid-state supercapacitor series connection；
Wherein, concatenated flexible solid is determined according to the electric signal of the multiple flexible friction nano generator output after parallel connection
The quantity of ultracapacitor, so that the electric signal of flexible solid-state supercapacitor input is sent out with the flexible friction nanometer
The electric signal of motor output matches.
7. self-charging system according to claim 5, wherein the second polymer fibrous web-like film layer and two layers described
It is arranged in parallel between the netted film layer of second carbon fiber.
8. a kind of wearable electronic based on flexible electric spinning reticular membrane, wherein the wearable electronic is from right
It is required that the self-charging system described in 5 obtains electricity.
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| CN107134943B (en) * | 2017-06-01 | 2019-04-05 | 苏州大学 | A kind of stretchable self-contained electric system, preparation method and wearable device |
| CN107502958B (en) * | 2017-07-10 | 2019-12-10 | 东华大学 | Breathable flexible pressure sensor based on friction nano generator and preparation method thereof |
| CN107493029B (en) * | 2017-07-10 | 2019-11-08 | 东华大学 | The electrostatic spinning fiber base friction nanometer power generator and its preparation of surface amino groups modification |
| CN107354588A (en) * | 2017-08-15 | 2017-11-17 | 东华大学 | A kind of method for strengthening Static Spinning polymer matrix friction nanometer power generator output voltage |
| CN109639175B (en) * | 2017-10-09 | 2020-09-15 | 北京纳米能源与系统研究所 | Friction nanometer generator, wearable sensor and preparation method of wearable sensor |
| CN109750403B (en) * | 2017-11-01 | 2021-05-11 | 北京纳米能源与系统研究所 | Power generation cloth, wearable device and sensor based on friction nano generator |
| CN109817469A (en) * | 2017-11-20 | 2019-05-28 | 北京纳米能源与系统研究所 | Supercapacitor, energy packet, self-charging energy packet and preparation method thereof |
| CN108233762B (en) * | 2018-03-22 | 2023-12-22 | 大连理工大学 | Flexible wearable friction nano generator capable of collecting mechanical energy in omnibearing multimode mode |
| CN108539837B (en) * | 2018-04-04 | 2020-02-14 | 中国地质大学（武汉） | Wearable graphene type electret self-generating and super-capacitor integrated woven cloth |
| CN109525140B (en) * | 2018-10-23 | 2020-02-11 | 东华大学 | Breathable knitted spacer fabric friction generator and preparation method thereof |
| CN109546890B (en) * | 2019-01-18 | 2020-07-31 | 清华大学 | Wet gas power generation method and device |
| CN110138257B (en) * | 2019-02-28 | 2020-05-12 | 苏州大学 | Friction nanometer generator, preparation method thereof and wearable device |
| CN112641425A (en) * | 2019-10-12 | 2021-04-13 | 四川大学 | Design and preparation of wearable flexible multi-parameter sensor |
| CN112342696B (en) * | 2020-10-29 | 2021-10-19 | 江苏联宇医疗器械有限公司 | Flexible non-woven material |
| CN113564804A (en) * | 2021-07-23 | 2021-10-29 | 天津工业大学 | Polyacrylonitrile piezoelectric material, preparation method and application thereof, and flexible piezoelectric nano generator |
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| CN103779885B (en) * | 2013-09-26 | 2015-12-23 | 北京纳米能源与系统研究所 | Constant voltage self-charging Power supply equipment and manufacture method thereof |
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