CN108039285A - A kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible - Google Patents
A kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible Download PDFInfo
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- CN108039285A CN108039285A CN201711015156.7A CN201711015156A CN108039285A CN 108039285 A CN108039285 A CN 108039285A CN 201711015156 A CN201711015156 A CN 201711015156A CN 108039285 A CN108039285 A CN 108039285A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible, including：Cortex solution of the 2 acetate groups ammonium acrylate acrylonitrile copolymer solution as coaxial electrostatic spinning of single-walled carbon nanotube will be contained；Sandwich layer solution using polymethyl methacrylate or styrene acrylonitrile copolymer solution as coaxial electrostatic spinning；Coaxial electrostatic spinning is carried out, obtains sub-micron fibers, through pre-oxidation, carbonization, obtains the sub-micron hollow carbon fiber of carbon nanotubes；With aniline in-situ polymerization, through vacuum filter, washing, it is dried in vacuo to obtain the final product.The present invention is easy to operate, it is not necessary to which complex device, is adapted to large-scale production；The combination electrode material of preparation has the characteristics that self-supporting, lightweight, flexibility, chemical property and cyclical stability are excellent, without collector, glue conductive additive, adhesive, electrode material for super capacitor is directly used as, extends application of the ultracapacitor in portable electronic products and intelligent clothing.
Description
Technical field
The invention belongs to electrode material for super capacitor technical field, more particularly to a kind of hollow compound super of light flexible
The preparation method of capacitor electrode material.
Background technology
Accelerate as global energy consumes, environmental pollution is on the rise, exploitation clean and effective, regenerative resource and new energy
Amount storage and switch technology are the hot spots studied at present.Ultracapacitor has power density height, follows as new type of energy storage device
The advantages that ring long lifespan, charge-discharge velocity are fast, environmentally protective, in fields such as defence and military, communications and transportation, the energy, electronic information
Have broad application prospects.
According to the difference of energy storage mechnism, ultracapacitor is divided into double layer capacitor and Faraday pseudo-capacitance device.Electric double layer
It using the interfacial electric double layer formed between electrode and electrolyte come storage energy, its electrode is usually high-specific surface area that capacitor, which is,
With the carbon material of high conductivity, common carbon electrode material mainly has mesoporous carbon, multi-stage porous carbon, carbon nanotubes, graphene, carbon to receive
Rice fiber, although research finds carbon electrode material power density height, specific capacitance and energy density are smaller.Faraday pseudo-capacitance device
It is to be broadly divided into metal using the chemisorbed/desorption and redox reaction of Rapid reversible come storage energy, its electrode material
Two major class of oxide and conducting polymer, has higher specific capacitance and energy density, but there are cyclical stability difference and power
The shortcomings that density is small.How by high power density, high circulation stablize carbon material and high specific capacitance metal oxide or conduction
Polymer combines, and prepares the heat that excellent cyclical stability, high-energy-density, high power density novel composite electrode material are research
Point.Carbon nanomaterial specific surface area is big, electrochemical stability is excellent, electric conductivity is high, and high (the theoretical specific capacitance of polyaniline specific capacitance
For 2000F/g), electric conductivity is high, convieniently synthesized, of low cost, chemical stability is good, therefore carbon nanomaterial/polyphenyl in recent years
Amine combination electrode material causes the broad interest of scientists.Chinese patent CN104465121A, CN106449146A,
CN102568848A discloses the method that electrochemical method prepares graphene oxide/polyaniline composite electrode material, electrochemistry side
Law article part is harsh, and large-scale production is difficult, and simultaneous oxidation graphene is there are poorly conductive, it is necessary to collector or conductive additive
As electrode material.Chinese patent CN101527202A, CN106710892A disclose oxidation situ aggregation method prepare graphene/
Then the method for polyaniline composite electrode material is suppressed and is used as electrode material on a current collector, it is necessary to add adhesive, conductive agent
Material.Chinese patent CN102093712A discloses liquid phase flame method and prepares spiral carbon nano-fiber, and then oxidant triggers aniline
Polymerization prepares spiral carbon nano-fiber/polyaniline composite electrode material.Chinese patent disclose CN105679554A disclose it is quiet
Electrospinning prepares coal-based carbon nanofiber, and then it is soft to prepare needle-shaped polyaniline/coal-based carbon nanofiber for oxidative polymerization method polymerization aniline
Property electrode material for super capacitor.Electrospinning device, technological operation are simple, it is possible to achieve large-scale production.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of hollow hybrid supercapacitor electrode material of light flexible
Preparation method, this method is easy to operate, it is not necessary to which complex device, is adapted to large-scale production；The combination electrode material tool of preparation
Have the characteristics of self-supporting, lightweight, flexibility, excellent chemical property and cyclical stability, without collector, glue conductive additive,
Adhesive, is directly used as electrode material for super capacitor, extends ultracapacitor in portable electronic products and intelligent clothing
Using.
A kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible of the present invention, including：
(1) single-walled carbon nanotube is added in solvent, ultrasonic disperse, the 2- acetate groups-ammonium acrylate-the third then added
Alkene lonitrile copolymer, stirring and dissolving, obtains the cortex solution of coaxial electrostatic spinning；By polymethyl methacrylate or styrene-acrylonitrile
Copolymer is added in solvent, and stirring and dissolving, obtains the sandwich layer solution of coaxial electrostatic spinning；Wherein single-walled carbon nanotube in cortex solution
Mass fraction be that the mass fraction of 1~5%, 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 15~21%；Sandwich layer
The mass fraction of polymethyl methacrylate or styrene acrylonitrile copolymer in solution is 26~32%；
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, obtain
Sub-micron fibers, then pre-oxidize in air atmosphere, are carbonized in nitrogen atmosphere, obtain the sub-micron hollow carbon of carbon nanotubes
Fiber；
(3) the sub-micron hollow carbon fiber for obtaining step (2) is added in solvent with aniline, initiator, catalyst, is carried out
In-situ polymerization, through being filtered by vacuum, washing, being dried in vacuo and obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor
Electrode material；Wherein aniline, initiator, the molar ratio of catalyst are 0.01~0.05：0.005~0.01：0.5~1.5.
Single-walled nanotube in the step (1) is carboxyl or amino modified carbon nanotubes, a diameter of 4~5nm, and length is
0.5~1.5um.
Solvent in the step (1) is dimethylformamide.
The time of ultrasonic disperse is 20~35min in the step (1).
The technological parameter of stirring and dissolving in the step (1)：Stirring and dissolving temperature is 50~75 DEG C, and the stirring and dissolving time is
12~24h.
The technological parameter of coaxial electrostatic spinning is in the step (2)：14~17kV of positive voltage, negative voltage -3~-1kV, connects
It is 10~20cm to receive distance, and it is 1mL/h to promote total speed, and the propulsion speed ratio of wherein cortex solution and sandwich layer solution is 1：1~
5：1.
The technological parameter of pre-oxidation is in the step (2)：Pre oxidation is 280~300 DEG C, preoxidation time 60
~90min.
The technological parameter of carbonization is in the step (2)：Carburizing temperature is 1100~1200 DEG C, carbonization time for 90~
120min。
A diameter of 0.7~1.5 μm of the sub-micron hollow carbon fiber of carbon nanotubes in the step (2), wall thickness are
100~180nm.
Initiator in the step (3) is ammonium persulfate.
Catalyst in the step (3) is sulfuric acid.
Solvent in the step (3) is deionized water.
The technological parameter of in-situ polymerization is in the step (3)：In-situ polymerization temperature is 0~5 DEG C, polymerization time for 22~
26h。
The process conditions of washing are with deionized water rinsing 4~6 times in the step (3).
Vacuum drying technological parameter is in the step (3)：Vacuum drying temperature is 60~80 DEG C, vacuum drying time
For 8~12h.
Light flexible hollow carbon fiber produced by the present invention/carbon nano-tube/poly aniline hybrid supercapacitor electrode material
In current density 1A/g, specific capacitance is 1195~1870F/g, and specific capacitance decay is less than 10% after 5000 circulations.
Beneficial effect
(1) preparation method of the invention is easy to operate, it is not necessary to which complex device, is adapted to large-scale production.
(2) present invention can effectively carry high-ratio surface using hollow carbon nano-fiber as combination electrode backing material
Product, increases polyaniline unit deposition, is conducive to improve specific capacitance；Hollow structure is conducive to increase electrode material and electrolysis at the same time
Effective contact area of matter solution, shortens ion diffusion length, reduces internal resistance.
(3) hollow carbon nano-fiber/compound self-supported membrane of carbon nanotube/nano polyaniline prepared by the present invention, has
The characteristics of self-supporting, lightweight, flexibility, excellent chemical property and cyclical stability, without collector, glue conductive additive, glue
Stick, can directly be used alone as electrode material for super capacitor, can prepare flexible sheet, line style supercapacitor applications in can
Wearing, mancarried electronic aid etc., expand its use scope, extend ultracapacitor in portable electronic products and intelligent clothing
Using.
Brief description of the drawings
Fig. 1 is the electron-microscope scanning figure of the sub-micron fibers in the embodiment of the present invention 1；
Fig. 2 is the electron-microscope scanning figure of the sub-micron hollow carbon fiber of the carbon nanotubes in the embodiment of the present invention 1；
Fig. 3 is obtained hollow carbon fiber in the embodiment of the present invention 1/carbon nano-tube/poly aniline hybrid supercapacitor electricity
The electron-microscope scanning figure of pole material；
Obtained hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode during Fig. 4 implements 1 for the present invention
The cyclic voltammetry curve of material.
Embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Scope.
Embodiment 1
(1) carboxy-modified single-walled carbon nanotube (4~5nm of diameter, 0.5~1.5um of length) is added in dimethyl sulfoxide (DMSO),
Ultrasonic disperse 25min, then adds 2- acetate groups-ammonium acrylate-acrylonitrile copolymer, and stirring and dissolving 12h at 75 DEG C, obtains
The cortex solution of coaxial electrostatic spinning；Styrene acrylonitrile copolymer is added in dimethyl sulfoxide (DMSO), stirring and dissolving 12h at 75 DEG C,
The sandwich layer solution of coaxial electrostatic spinning is obtained, the mass fraction of carboxy-modified single-walled carbon nanotube is 1.2% wherein in cortex solution,
The mass fraction of 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 17%；Styrene-acrylonitrile copolymerization in sandwich layer solution
The mass fraction of thing is 28%.
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, apply
Positive voltage 15kv, negative voltage -1kv, the propulsion speed 0.75mL/h of cortex solution, the propulsion speed 0.25mL/h of sandwich layer solution,
Distance 15cm is received, obtains sub-micron fibers, then pre-oxidation treatment 60min, high pure nitrogen gas at 280 DEG C in air atmosphere
Be carbonized 90min in atmosphere at 1150 DEG C, obtains 0.9~1.0 μm of diameter, in the sub-micron of the carbon nanotubes of 120~130nm of wall thickness
Empty carbon fiber.
(3) the sub-micron hollow carbon fiber that step (2) obtains and aniline, initiator ammonium persulfate, catalyst sulfuric acid are added
Enter in deionized water, carry out in-situ polymerization 24h at 0 DEG C, vacuum filtration, with deionized water rinsing 5 times, 70 DEG C of vacuum drying 10h,
Obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode material；Wherein aniline, initiator, catalyst
Molar ratio is 0.03mol：0.0075mol：1mol.
To obtained in the present embodiment sub-micron fibers, the sub-micron hollow carbon fiber of carbon nanotubes, hollow carbon fiber/
Carbon nano-tube/poly aniline hybrid supercapacitor electrode material carries out electron-microscope scanning test respectively, as a result respectively as shown in Figure 1, Figure 2,
Shown in Fig. 3, it is seen that the sub-micron fibers even structure that coaxial electrostatic spinning is prepared, a diameter of 0.9~1.4 μm, hollow carbon
Nanofibrous structures are uniform, and a diameter of 120~130nm, polyaniline nano-rod is uniformly deposited on hollow carbon fiber/carbon nanotubes
The surfaces externally and internally of composite material, can effectively improve the deposition of active material and its contact area with electrolyte.
The hollow carbon fiber obtained to the present embodiment/carbon nano-tube/poly aniline hybrid supercapacitor electrode material carries out
Cyclic voltammetry, the results are shown in Figure 4, it is seen that obvious redox peaks, corresponding reduction-state, conductive state and oxidized state
Transformation, the area of cyclic voltammetry curve increases with the increase of current density and shape remains unchanged, illustrate hollow carbon fibre
Dimension/carbon nano-tube/poly aniline hybrid supercapacitor electrode material has good multiplying power capacitance characteristic.
The hollow carbon fiber that the present embodiment obtains/carbon nano-tube/poly aniline hybrid supercapacitor electrode material is in electric current
During density 1A/g, specific capacitance 1342F/g, specific capacitance decay is less than 10% after 5000 circulations.
Embodiment 2
(1) carboxy-modified single-walled carbon nanotube (4~5nm of diameter, 0.5~1.5um of length) is added in dimethyl sulfoxide (DMSO),
Ultrasonic disperse 25min, then adds 2- acetate groups-ammonium acrylate-acrylonitrile copolymer, and stirring and dissolving 12h at 75 DEG C, obtains
The cortex solution of coaxial electrostatic spinning；Styrene acrylonitrile copolymer is added in dimethyl sulfoxide (DMSO), stirring and dissolving 12h at 75 DEG C,
The sandwich layer solution of coaxial electrostatic spinning is obtained, the mass fraction of carboxy-modified single-walled carbon nanotube is 1.2% wherein in cortex solution,
The mass fraction of 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 17%；Styrene-acrylonitrile copolymerization in sandwich layer solution
The mass fraction of thing is 28%.
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, apply
Positive voltage 15kv, negative voltage -1kv, the propulsion speed 0.5mL/h of cortex solution, the propulsion speed 0.5mL/h of sandwich layer solution, connects
Distance 15cm is received, obtains sub-micron fibers, then pre-oxidation treatment 60min, high pure nitrogen atmosphere at 280 DEG C in air atmosphere
In be carbonized at 1150 DEG C 90min, obtain 1.0~1.1 μm of diameter, the sub-micron of the carbon nanotubes of 110~120nm of wall thickness is hollow
Carbon fiber.
(3) the sub-micron hollow carbon fiber that step (2) obtains and aniline, initiator ammonium persulfate, catalyst sulfuric acid are added
Enter in deionized water, carry out in-situ polymerization 24h at 0 DEG C, vacuum filtration, with deionized water rinsing 5 times, 70 DEG C of vacuum drying 10h,
Obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode material；Wherein aniline, initiator, catalyst
Molar ratio is 0.03mol：0.0075mol：1mol.
The hollow carbon fiber that the present embodiment obtains/carbon nano-tube/poly aniline hybrid supercapacitor electrode material is in electric current
During density 1A/g, specific capacitance 1457F/g, specific capacitance decay is less than 10% after 5000 circulations.
Embodiment 3
(1) carboxy-modified single-walled carbon nanotube (4~5nm of diameter, 0.5~1.5um of length) is added in dimethyl sulfoxide (DMSO),
Ultrasonic disperse 25min, then adds 2- acetate groups-ammonium acrylate-acrylonitrile copolymer, and stirring and dissolving 12h at 75 DEG C, obtains
The cortex solution of coaxial electrostatic spinning；Styrene acrylonitrile copolymer is added in dimethyl sulfoxide (DMSO), stirring and dissolving 12h at 75 DEG C,
The sandwich layer solution of coaxial electrostatic spinning is obtained, the mass fraction of carboxy-modified single-walled carbon nanotube is 1.2% wherein in cortex solution,
The mass fraction of 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 17%；Styrene-acrylonitrile copolymerization in sandwich layer solution
The mass fraction of thing is 28%.
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, apply
Positive voltage 15kv, negative voltage -1kv, the propulsion speed 0.25mL/h of cortex solution, the propulsion speed 0.75mL/h of sandwich layer solution,
Distance 15cm is received, obtains sub-micron fibers, then pre-oxidation treatment 60min, high pure nitrogen gas at 280 DEG C in air atmosphere
Be carbonized 90min in atmosphere at 1150 DEG C, obtains 1.0~1.2 μm of diameter, in the sub-micron of the carbon nanotubes of 100~110nm of wall thickness
Empty carbon fiber.
(3) the sub-micron hollow carbon fiber that step (2) obtains and aniline, initiator ammonium persulfate, catalyst sulfuric acid are added
Enter in deionized water, carry out in-situ polymerization 24h at 0 DEG C, vacuum filtration, with deionized water rinsing 5 times, 70 DEG C of vacuum drying 10h,
Obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode material；Wherein aniline, initiator, catalyst
Molar ratio is 0.03mol：0.0075mol：1mol.
The hollow carbon fiber that the present embodiment obtains/carbon nano-tube/poly aniline hybrid supercapacitor electrode material is in electric current
During density 1A/g, specific capacitance 1631F/g, specific capacitance decay is less than 10% after 5000 circulations.
Embodiment 4
(1) carboxy-modified single-walled carbon nanotube (4~5nm of diameter, 0.5~1.5um of length) is added in dimethyl sulfoxide (DMSO),
Ultrasonic disperse 25min, then adds 2- acetate groups-ammonium acrylate-acrylonitrile copolymer, and stirring and dissolving 12h at 75 DEG C, obtains
The cortex solution of coaxial electrostatic spinning；Styrene acrylonitrile copolymer is added in dimethyl sulfoxide (DMSO), stirring and dissolving 12h at 75 DEG C,
The sandwich layer solution of coaxial electrostatic spinning is obtained, the mass fraction of carboxy-modified single-walled carbon nanotube is 1.2% wherein in cortex solution,
The mass fraction of 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 17%；Styrene-acrylonitrile copolymerization in sandwich layer solution
The mass fraction of thing is 28%.
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, apply
Positive voltage 15kv, negative voltage -1kv, the propulsion speed 0.75mL/h of cortex solution, the propulsion speed 0.25mL/h of sandwich layer solution,
Distance 15cm is received, obtains sub-micron fibers, then pre-oxidation treatment 60min, high pure nitrogen gas at 280 DEG C in air atmosphere
Be carbonized 90min in atmosphere at 1150 DEG C, obtains 0.9~1.0 μm of diameter, in the sub-micron of the carbon nanotubes of 120~130nm of wall thickness
Empty carbon fiber.
(3) the sub-micron hollow carbon fiber that step (2) obtains and aniline, initiator ammonium persulfate, catalyst sulfuric acid are added
Enter in deionized water, carry out in-situ polymerization 24h at 0 DEG C, vacuum filtration, with deionized water rinsing 5 times, 70 DEG C of vacuum drying 10h,
Obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode material；Wherein aniline, initiator, catalyst
Molar ratio is 0.05mol：0.01mol：1mol.
The hollow carbon fiber that the present embodiment obtains/carbon nano-tube/poly aniline hybrid supercapacitor electrode material is in electric current
During density 1A/g, specific capacitance 1412F/g, specific capacitance decay is less than 10% after 5000 circulations.
Claims (9)
1. a kind of preparation method of light flexible hollow carbon hybrid supercapacitor electrode material, including：
(1) single-walled carbon nanotube is added in solvent, ultrasonic disperse, the 2- acetate groups-ammonium acrylate-acrylonitrile then added
Copolymer, stirring and dissolving, obtains the cortex solution of coaxial electrostatic spinning；Polymethyl methacrylate or styrene-acrylonitrile are copolymerized
Thing is added in solvent, and stirring and dissolving, obtains the sandwich layer solution of coaxial electrostatic spinning；The matter of single-walled carbon nanotube wherein in cortex solution
Amount fraction is that the mass fraction of 1~5%, 2- acetate groups-ammonium acrylate-acrylonitrile copolymer is 15~21%；Sandwich layer solution
In polymethyl methacrylate or styrene acrylonitrile copolymer mass fraction be 26~32%；
(2) the cortex solution of the coaxial electrostatic spinning obtained using step (1) and sandwich layer solution carry out coaxial electrostatic spinning, obtain sub-micro
Rice fiber, then pre-oxidizes in air atmosphere, is carbonized in nitrogen atmosphere, and the sub-micron hollow carbon for obtaining carbon nanotubes is fine
Dimension；
(3) the sub-micron hollow carbon fiber for obtaining step (2) is added in solvent with aniline, initiator, catalyst, is carried out in situ
Polymerization, through being filtered by vacuum, washing, being dried in vacuo and obtain hollow carbon fiber/carbon nano-tube/poly aniline hybrid supercapacitor electrode
Material；Wherein aniline, initiator, the molar ratio of catalyst are 0.01~0.05：0.005~0.01：0.5~1.5.
2. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：Single-walled nanotube in the step (1) is carboxyl or amino modified carbon nanotubes, a diameter of 4~5nm, length
For 0.5~1.5um；Solvent is dimethylformamide.
3. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：The time of ultrasonic disperse is 20~35min in the step (1)；The technological parameter of stirring and dissolving：Stirring and dissolving temperature
Spend for 50~75 DEG C, the stirring and dissolving time is 12~24h.
4. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：The technological parameter of coaxial electrostatic spinning is in the step (2)：14~17kV of positive voltage, negative voltage -3~-1kV, connects
It is 10~20cm to receive distance, and it is 1mL/h to promote total speed, and the propulsion speed ratio of wherein cortex solution and sandwich layer solution is 1：1~
5：1.
5. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：The technological parameter of pre-oxidation is in the step (2)：Pre oxidation is 280~300 DEG C, and preoxidation time is
60~90min；The technological parameter of carbonization is：Carburizing temperature is 1100~1200 DEG C, and carbonization time is 90~120min.
6. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：A diameter of 0.7~1.5 μm of the sub-micron hollow carbon fiber of carbon nanotubes in the step (2), wall thickness are
100~180nm.
7. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：Initiator in the step (3) is ammonium persulfate；Catalyst is sulfuric acid；Solvent is deionized water.
8. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：The technological parameter of in-situ polymerization is in the step (3)：In-situ polymerization temperature is 0~5 DEG C, polymerization time 22
~26h.
9. a kind of preparation method of the hollow hybrid supercapacitor electrode material of light flexible according to claim 1, its
It is characterized in that：Vacuum drying technological parameter is in the step (3)：Vacuum drying temperature is 60~80 DEG C, during vacuum drying
Between be 8~12h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109326453A (en) * | 2018-09-10 | 2019-02-12 | 中原工学院 | A kind of polypyrrole composite electrode material for super capacitor and preparation method thereof based on electrostatic spinning nano fiber resultant yarn technology |
| CN109326450A (en) * | 2018-09-10 | 2019-02-12 | 中原工学院 | It is a kind of flexibility carbon fiber-based dye-sensitized solar cells to electrode material and preparation method |
| CN109727783A (en) * | 2019-01-14 | 2019-05-07 | 湖南科技大学 | A kind of carbon hollow ball composite material of carbon paper load, preparation method and applications |
| CN110055622A (en) * | 2019-04-04 | 2019-07-26 | 东华大学 | A kind of preparation method of hollow structure porous carbon nanofiber |
| CN111785527A (en) * | 2020-07-17 | 2020-10-16 | 广德天运新技术股份有限公司 | Pseudo-capacitive fibrous supercapacitor without blank volume in electrode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| CN106968023A (en) * | 2017-05-05 | 2017-07-21 | 郑州大学 | Conducting polymer composite fibre with skin-core structure and preparation method thereof |
-
2017
- 2017-10-26 CN CN201711015156.7A patent/CN108039285A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433614A (en) * | 2011-08-23 | 2012-05-02 | 东华大学 | Preparation method of low-shrinkage high-strength carbon nanofiber |
| CN106968023A (en) * | 2017-05-05 | 2017-07-21 | 郑州大学 | Conducting polymer composite fibre with skin-core structure and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| ANQI JU,ET AL.: ""Preparation of hollow carbon submicro-fibers with controllable wall thicknesses from acrylonitrile copolymer"", 《TEXTILE RESEARCH JOURNAL》 * |
| SHUANGYAN GAO,ET AL.: ""Polyaniline Nanorods Grown on Hollow Carbon Fibers as High-Performance Supercapacitor Electrodes"", 《CHEMELECTROCHEM》 * |
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| CN109326450A (en) * | 2018-09-10 | 2019-02-12 | 中原工学院 | It is a kind of flexibility carbon fiber-based dye-sensitized solar cells to electrode material and preparation method |
| CN109326453B (en) * | 2018-09-10 | 2020-09-29 | 中原工学院 | Polypyrrole supercapacitor composite electrode material and preparation method thereof |
| CN109727783A (en) * | 2019-01-14 | 2019-05-07 | 湖南科技大学 | A kind of carbon hollow ball composite material of carbon paper load, preparation method and applications |
| CN110055622A (en) * | 2019-04-04 | 2019-07-26 | 东华大学 | A kind of preparation method of hollow structure porous carbon nanofiber |
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| CN111785527A (en) * | 2020-07-17 | 2020-10-16 | 广德天运新技术股份有限公司 | Pseudo-capacitive fibrous supercapacitor without blank volume in electrode and preparation method thereof |
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