CN106531474A - Linear electrode and preparation method therefor by adopting electrospinning technique - Google Patents
Linear electrode and preparation method therefor by adopting electrospinning technique Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001523 electrospinning Methods 0.000 title claims abstract 5
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 229920005594 polymer fiber Polymers 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 34
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229960002415 trichloroethylene Drugs 0.000 claims description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract 1
- 239000002121 nanofiber Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000000835 fiber Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 238000005255 carburizing Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000009975 flexible effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a linear electrode and a preparation method therefor by adopting an electrospinning technique. The preparation method specifically comprises the steps of dissolving a high-molecular polymer into an effective organic solvent, and preparing a polymer thin film by adopting the electrospinning technique; peeling off the polymer thin film from a collector, and preparing the thin film into polymer fibers in a rolling or entwisting manner; and next, performing pre-oxidization and carbonization on the polymer fibers in sequence to obtain the linear electrode with a diameter of 10-500[mu]m. The carbonized polymer nanofibers prepared by adopting the electrospinning technique have the advantages of large specific areas, rich pore-channel structures and the like; in addition, the preparation method is simple in equipment and process, low in cost, short in preparation period, pollution-free in process, relatively low in cost of the raw materials, and easy to realize batch production; and the linear electrode provided by the invention has the advantages of high conductivity, high flexibility, length controllability, and the like.
Description
Technical field
The present invention relates to wire electrode field of material preparation, more particularly it relates to a kind of adopt electrostatic spinning skill
Art prepares the method and wire electrode of wire electrode.
Background technology
And the wearable electronic product that be well known integrated with intelligent textile or electronic product and yarn fabric, now
The extensive concern from science and industrial circle is attracted.It is in order that wearable electronic product becomes a reality, high-performance, flexible
Property, the wearable energy storage device of security are prerequisite conditions.So in recent years, the elasticity of membranaceous or wire surpasses
Level capacitor and battery are widely studied.Relative to membrane structure, wire energy storage device be easier to compile into yarn fabric or its
His structure, and requirement of the wearer to comfort level can be met, with unique potential application.
At present in wire electrode material for super capacitor field, CNT and Graphene are intrinsic high flexible due to them
Property, low-density, remarkable electronics and thermoelectricity conductance and it is studied the most extensive.Continuous carbon can be prepared using wet-spinning techniques
Nanotube and Graphene line, are used as the electrode of ultracapacitor, except also having very high electricity with good pliability
Chemical property, can also have good cyclical stability.Meanwhile, capacitance behavior and porous electrode and the electricity of double layer capacitor
Between solution liquid ion, electrostatic reaction is relevant, so the specific surface area of electrode has decisive role to capacity.However, due to carbon nanometer
The poor wellability of the aggregation of pipe and Graphene and solid-state electrolytic solution, even if CNT and Graphene have big specific surface area
Also it is not fully used.
The content of the invention
Instant invention overcomes the deficiencies in the prior art, there is provided a kind of method that employing electrostatic spinning technique prepares wire electrode
And wire electrode, to expect to obtain the big lineation electrode of specific surface area height, capacity.
To solve above-mentioned technical problem, one embodiment of the present invention is employed the following technical solutions：
High molecular polymer is specifically dissolved in which effective by a kind of method that employing electrostatic spinning technique prepares wire electrode
In organic solvent, thin polymer film is prepared using electrostatic spinning technique, adopted after thin polymer film is peeled from collector
Film is made polymer fiber by volume or the mode twisted with the fingers, and polymer fiber is sequentially passed through pre-oxidation subsequently and is carbonized, obtain line
Shape electrode.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, the high molecular polymer be polyacrylonitrile,
One or more in polyvinylpyrrolidone, polyvinyl butyral resin, polyvinyl alcohol.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and the molecular weight of the high molecular polymer is
10000～500000.If polyacrylonitrile molecular weight is less than 10000, spinning cannot carry out or have miniliform fiber and deposit
；If polyacrylonitrile molecular weight is more than 500000, the viscosity of spinning solution is too big, it is impossible to which spinning or the fiber prepared are straight
Footpath is larger.Preferably, described polyacrylonitrile molecular weight is 50000～200000.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and effective organic solvent is chloroform, dichloro
Methane, trichloro ethylene, tetrachloroethanes, 1-METHYLPYRROLIDONE, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, acetone,
One or more in ethanol, water.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and it is effectively organic molten that high molecular polymer is dissolved in which
The concentration of the polymer solution obtained by agent is 1～30wt%.If the concentration of polymer solution is less than 1wt%, can not the company of spinning
Continuous polymer fiber；If the concentration of polymer solution is more than 30wt%, many drops on spun filament, occur.It is excellent
Choosing, the concentration of described polymer solution is 10～15wt%.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and the technological parameter of the electrostatic spinning technique is such as
Under：Voltage is 5～25kV, and pushing speed is 0.1～4mL/h, and distance of the needle point away from receiver is 5～25cm, and receiver is aluminium
Paper tinsel.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and the thickness of the thin polymer film is 1～50 μ
m。
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, it is described pre-oxidation refer to by polymer fiber with
The heating rate of 0.5～25 DEG C/min is warming up to 250～400 DEG C, is then incubated 1～6h at such a temperature.If heating rate is little
In 0.5 DEG C/min, then the time for pre-oxidizing is oversize；If heating rate is more than 25 DEG C/min, cyclization may first occur
After there is oxidation reaction, cause oxidization fiber skin-core structure.The temperature of pre-oxidation is less than 250 DEG C, then can not complete pre-oxidation；
If the temperature of pre-oxidation is more than 400 DEG C, fiber may be melted or be burnt because overheated；Preferably, described pre-oxidation temperature
Spend for 200～300 DEG C, temperature retention time is 2～3h.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, and the carbonization is referred to the polymerization after pre-oxidation
Fibres under an inert atmosphere, are warming up to 600～1500 DEG C with the heating rate of 1～20 DEG C/min, then protect at such a temperature
0.5～8h of temperature.Inert gas can use nitrogen or argon gas.If heating rate is less than 1 DEG C/min, carbonization time is oversize；
If heating rate is more than 20 DEG C/min, heating rate is too fast, and the reaction speeds such as dehydrogenation, dehydration can be caused to accelerate, fiber is caused
Space, crackle are produced in structure；Preferably, carbonization is warming up to 600～1500 DEG C with the heating rate of 1～5 DEG C/min.Carbonization
Temperature is 600～1500 DEG C, if carburizing temperature is less than 600 DEG C, the non-carbon element such as H, N cannot be deviate from from fiber totally；If
Carburizing temperature is more than 1500 DEG C, then the intensity of carbon fiber can decline；Preferably, described carburizing temperature is 750～1100 DEG C, is protected
The warm time is 1～2h.
Using wire electrode obtained in above-mentioned preparation method, its a diameter of 10～500 μm.
Above-mentioned employing electrostatic spinning technique is prepared in the method for wire electrode, can also be by SiO2Microballoon is dissolved in and above-mentioned effectively having
After suspension is formed in machine solvent, according to mass ratio 1:9～10 the suspension is mixed with polymer solution after carry out electrostatic again
Spinning.The film for obtaining is twisted into silk and is pre-oxidized, the silk for having pre-oxidized is soaked in into the hydrofluoric acid that concentration is 10wt% subsequently
Removing SiO in solution2Microballoon, then cleaned with absolute ethyl alcohol and deionized water, it is carbonized after being dried, wire multilayer is obtained
Secondary porous carbon materials electrode, aperture is in the range of 90～110nm.
Compared with prior art, one of beneficial effects of the present invention are：The polymer nano prepared using electrostatic spinning technique
Rice fiber, after carbonization, the carbon fiber has the advantages that specific surface area height, pore passage structure enrich, and its equipment, process is simple, into
This is cheap, and short preparation period, process are pollution-free, and cost of material used is relatively low, it is easy to produce in batches.The wire that the present invention is provided
Electrode has the advantages that good conductivity, pliability be good, length is controllable.
Description of the drawings
Fig. 1 is the SEM figures of wire electrode prepared by embodiment 4.
Fig. 2 is the amplification SEM figures of wire electrode prepared by embodiment 4.
Fig. 3 be embodiment 4 prepare wire electrode be used as all solid state symmetric capacitor electrode when in different current densities
Under charge and discharge electrograph.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention
Limit the present invention.
Embodiment 1
The polyacrylonitrile that molecular weight is 10000 is dissolved in DMF (DMF), in the rotating speed of 1000rpm
Lower magnetic agitation 5h, the concentration of gained polyacrylonitrile solution is 30wt%, then prepares polyacrylonitrile using electrostatic spinning technique
Fiber, the technological parameter of electrostatic spinning are as follows：Voltage 5kV, pushing speed is 0.1mL/h, and distance of the needle point away from receiver is
10cm, receiver are aluminium foil, obtain polyacrylonitrile film, about 1.5 μm of its thickness.The polyacrylonitrile film is twisted into diameter about
10 μm of silk, is then heated to 250 DEG C with the heating rate of 0.5 DEG C/min in air atmosphere, and insulation 1h is aoxidized；Then
600 DEG C are heated to the heating rate of 1 DEG C/min in a nitrogen atmosphere, insulation 5h is carbonized, and wire carbon is obtained after cooling
Material electrodes, about 9 μm of diameter.The lineation electrode for obtaining has good cyclicity and high rate performance, in 0.1A/g current densities
Under discharge capacity reach 186.2F/g, it is 86% that 2000 capability retentions are circulated under 0.5A/g current densities.
Embodiment 2
The polyacrylonitrile that molecular weight is 150000 is dissolved in DMF (DMF), in the rotating speed of 1000rpm
Lower magnetic agitation 5h, the concentration of gained polyacrylonitrile solution is 20wt%, then prepares polyacrylonitrile using electrostatic spinning technique
Fiber, the technological parameter of electrostatic spinning are as follows：Voltage 25kV, pushing speed is 1mL/h, and distance of the needle point away from receiver is
10cm, receiver are aluminium foil, obtain polyacrylonitrile film, about 20 μm of its thickness.Polyacrylonitrile film is twisted into diameter about 200
μm silk, be then heated to 280 DEG C with the heating rate of 5 DEG C/min in air atmosphere, insulation 3h aoxidized；Then in nitrogen
1000 DEG C are heated to the heating rate of 5 DEG C/min under gas atmosphere, insulation 4h is carbonized, and wire material with carbon element is obtained after cooling
Electrode, about 190 μm of diameter.The lineation electrode for obtaining has good cycle performance, and the electric discharge under 0.1A/g current densities is held
Amount reaches 242.8F/g, and it is 91% that 3000 capability retentions are circulated under 0.8A/g current densities.
Embodiment 3
The polyacrylonitrile that molecular weight is 500000 is dissolved in DMF (DMF), in the rotating speed of 1000rpm
Lower magnetic agitation 5h, the concentration of gained polyacrylonitrile solution is 10wt%, then prepares polyacrylonitrile using electrostatic spinning technique
Fiber, the technological parameter of electrostatic spinning are as follows：Voltage 15kV, pushing speed is 2mL/h, and distance of the needle point away from receiver is
10cm, receiver are aluminium foil, obtain polyacrylonitrile film, about 50 μm of its thickness.Polyacrylonitrile film is twisted into diameter about 500
μm silk, be then heated to 300 DEG C with the heating rate of 25 DEG C/min in air atmosphere, insulation 6h aoxidized；Then exist
1500 DEG C are heated to the heating rate of 10 DEG C/min under nitrogen atmosphere, insulation 2h is carbonized, and wire carbon is obtained after cooling
Material electrodes, about 480 μm of diameter.The lineation electrode for obtaining has good high rate performance, under 0.1A/g current densities first
Discharge capacity reaches 222.4F/g, and it is 83% that 5000 capability retentions are circulated under 1A/g current densities.
Embodiment 4
The polyacrylonitrile that molecular weight is 250000 be dissolved in 1-METHYLPYRROLIDONE (NMP) to be obtained mass fraction being 10%
Polyacrylonitrile solution, by the SiO that particle diameter is 100nm2Microballoon is dissolved in 1-METHYLPYRROLIDONE (NMP) and obtains mass fraction for 5%
SiO2Suspension, then takes 4.75g polyacrylonitrile solutions and 0.5g SiO2Suspension mixes, the magnetic force under 1000rpm rotating speeds
Stirring 3h, then prepares SiO using electrostatic spinning technique2- polyacrylonitrile fibre, the technological parameter of electrostatic spinning are as follows：Voltage
15V, pushing speed are 2mL/h, and distance of the needle point away from receiver is 15cm, and receiver is aluminium foil, obtains SiO2- polyacrylonitrile is thin
Film, about 20 μm of its thickness.By SiO2- polyacrylonitrile film is twisted a diameter of 200 μm of silk.Then in air atmosphere with 5
DEG C/heating rate of min is heated to 300 DEG C, insulation 1h is aoxidized.The silk for having pre-processed is soaked in concentration subsequently is
Removing SiO in the hydrofluoric acid solution of 10wt%2Microballoon, then cleaned with absolute ethyl alcohol and deionized water, 6h is dried at 80 DEG C
Afterwards.Then 1000 DEG C are heated to the heating rate of 1 DEG C/min in a nitrogen atmosphere, are incubated 1h, aperture is obtained after cooling is
The multi-level porous carbon materials electrode of wire of 100nm, its microstructure is as shown in figure 1, amplify SEM figures as shown in Figure 2.Fig. 3 is
When the wire electrode of the embodiment is used as all solid state symmetric capacitor electrode, discharge and recharge of the electrode under different current densities
Figure, from figure 3, it can be seen that the lineation electrode for obtaining has good high rate performance, the electric discharge under 0.1A/g current densities is held
Amount reaches 162.4F/g, and it is 82.6% that 3000 capability retentions are circulated under 0.5A/g current densities.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability
Field technique personnel can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in the application public affairs
Within the spirit opened and spirit.More specifically, in the range of disclosure, can be to the group of theme composite configuration
Various modifications and improvement are carried out into part and/or layout.Except the modification that carries out to building block and/or layout and in addition to improving,
To those skilled in the art, other purposes also will be apparent.
Claims (10)
1. a kind of method that employing electrostatic spinning technique prepares wire electrode, it is characterised in that high molecular polymer is dissolved in which has
In effect organic solvent, thin polymer film is prepared using electrostatic spinning technique, is adopted after thin polymer film is peeled from collector
Film is made into polymer fiber with volume or the mode twisted with the fingers, polymer fiber is sequentially passed through into pre-oxidation subsequently and is carbonized, obtained
Wire electrode.
2. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that the height
Molecularly Imprinted Polymer be polyacrylonitrile, polyvinylpyrrolidone, polyvinyl butyral resin, one or more in polyvinyl alcohol.
3. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that the height
The molecular weight of Molecularly Imprinted Polymer is 10000～500000.
4. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that described to have
Effect organic solvent be chloroform, dichloromethane, trichloro ethylene, tetrachloroethanes, 1-METHYLPYRROLIDONE, N,N-dimethylformamide,
One or more in DMAC N,N' dimethyl acetamide, acetone, ethanol, water.
5. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that macromolecule
It is 1～30wt% that polymer is dissolved in the concentration of its polymer solution obtained by effective organic solvent.
6. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that described quiet
The technological parameter of Electrospinning is as follows：Voltage be 5～25kV, pushing speed be 0.1～4mL/h, needle point away from receiver away from
From for 5～25cm, receiver is aluminium foil.
7. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that described poly-
The thickness of compound film is 1～50 μm.
8. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that described pre-
Oxidation refers to and for polymer fiber to be warming up to 250～400 DEG C with the heating rate of 0.5～25 DEG C/min, then at such a temperature
1～6h of insulation.
9. the method that employing electrostatic spinning technique according to claim 1 prepares wire electrode, it is characterised in that the carbon
Change referred to the polymer fiber after pre-oxidation under an inert atmosphere, 600 are warming up to the heating rate of 1～20 DEG C/min～
1500 DEG C, 0.5～8h is then incubated at such a temperature.
10. using a diameter of 10～500 μm obtained in the preparation method described in claim 1～9 any one of wire electrode.
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