CN106571236A - Nano-palygorskite modified polyaniline carbon nanotube composite electrode material - Google Patents
Nano-palygorskite modified polyaniline carbon nanotube composite electrode material Download PDFInfo
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- CN106571236A CN106571236A CN201610929776.0A CN201610929776A CN106571236A CN 106571236 A CN106571236 A CN 106571236A CN 201610929776 A CN201610929776 A CN 201610929776A CN 106571236 A CN106571236 A CN 106571236A
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- palygorskite
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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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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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 invention discloses a nano-palygorskite modified polyaniline carbon nanotube composite electrode material, and the material is made of the following raw materials by weight: 10-12 parts of multiwalled carbon nanotubes, 1.5-1.6 parts of lauryl sodium sulfate, an appropriate amount of deionized water, an appropriate amount of absolute ethyl alcohol, an appropriate amount of chloroform, 14-15 parts of polyoxyethylene, 12-13 parts of DL-Camphorsulfonic acid, 0.2-0.3 parts of palygorskite, an appropriate amount of hydrochloric acid solution with the concentration 1 mol/L, 10-12 parts of phenylamine, and 12.6-1.3 parts of ammonium persulfate. The electrostatic spinning fibrous membrane is excellent in aperture distribution, can provide a good channel for the diffusion of electrolyte ions, and is good in specific capacitance. A super-capacitor made of the material is excellent in electrochemical performances.
Description
Technical field
The present invention relates to capacitor technology field, more particularly to a kind of nanometer palygorskite modified polyaniline CNT is compound
Electrode material.
Background technology
Ultracapacitor also known as electrochemical capacitor, with power density it is big, have extended cycle life, easy maintenance and cost
The features such as relative moderate.Ultracapacitor has the energy density and than battery higher power bigger than traditional dielectric capacitor
Density, has broad application prospects in fields such as emergency power supply, hybrid power, digital product, telecommunications.CNT since
Since 1991 are found, due to excellent mechanical property, thermal property, electric conductivity, and scientist's research is become
Focus.CNT is preferable composite addition phase, with up to more than 1000 draw ratio, simultaneously because sp2
Orbital hybridization forms a large amount of delocalization p electronics, and electric conductivity is excellent.Electricity of the polyaniline as ultracapacitor electric conductive polymer
The advantages of pole material, environmental stability, high conductivity due to being readily synthesized, good, application has been widely studied.However, poly-
Aniline is because the shortcomings of Volume Changes are greatly with poor cycle charging/discharge capability, limits it in electrode of super capacitor material
Application in terms of material.These problems can be solved by the way that polyaniline is merged with c-based nanomaterial, so as to realize electrification
Learn the synergy of double layer capacitor and fake capacitance capacitor.Therefore, the nano-carbon material of bigger serface and satisfactory electrical conductivity
It is used as support material to obtain the combination electrode of high-performance and long circulation life.
《Carbon nano-tube/poly aniline/Graphene composite nanometer carbon paper and its electrochemical capacitor performance》Pass through vacuum in one text
The method of suction filtration prepares carbon nanotube paper, and a volt-ampere electrochemicial oxidation is circulated to it, with the electrochemicial oxidation
Carbon nanotube paper based on, using electrochemical polymer deposition polyaniline, subsequently adsorb Graphene, prepare and there is sandwich
Carbon nano-tube/poly aniline/Graphene the composite nanometer carbon paper of sandwich structure, the compound carbon paper has good capacitance characteristic, big
Current charge-discharge electrical characteristics and good stable circulation performance.But operating procedure is complicated, it is difficult to control the structure of extrusion coating paper, with
As for being difficult to improve its specific surface area, the raising of specific capacitance is limited；And because the carbon produced in actual production process is received
Mitron can all remain the catalyst impurities of a part, and some amorphous carbon, and the presence of these impurity limits carbon nanometer
The use of pipe, using sour purifying carbon nano-tube in article, while nitration mixture process most of amorphous carbon and gold is eliminated
Metal particles, but processing procedure is loaded down with trivial details, it is seriously polluted, while some functional groups are have also been introduced, the presence pair of these functional groups
The structure of CNT causes certain destruction, so as to produce certain impact to performance, limits its performance；To sum up institute
State, need to carry out certain improvement to process meanses such that it is able to which prepared operation is controllable, and electric conductivity is strong, specific surface area is big, ratio is electric
Hold big electrode material for super capacitor, meet the demand of development in science and technology.
The content of the invention
The object of the invention is exactly to make up the defect of prior art, there is provided a kind of nanometer palygorskite modified polyaniline carbon is received
Mitron combination electrode material.
The present invention is achieved by the following technical solutions：
A kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, is prepared by the raw materials in：Many walls
CNT 10-12, lauryl sodium sulfate 1.5-1.6, appropriate deionized water, appropriate absolute ethyl alcohol, appropriate chloroform, polyoxygenated
Ethene 14-15, DL camphorsulfonic acid 12-13, palygorskite 0.2-0.3,1mol/L hydrochloric acid solution is appropriate, aniline 10-12, over cure
Sour ammonium 12.6-1.3.
A kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, prepared by following concrete grammar and
Into：
（1）Multi-walled carbon nano-tubes is placed on into graphite crucible stove, in being placed in graphitizing furnace, it is vacuumized, with 10-15 DEG C/
Min is warming up to 2800 DEG C, is incubated 20-20 hours, and natural cooling obtains graphitized carbon nano pipe；By above-mentioned graphitized carbon nano
Pipe was put in ball mill with the speed ball milling 90-120 minutes of 200-300 turn/part, and addition is dissolved in the 25-30 times of deionized water measured
Lauryl sodium sulfate, after ultrasonic 20-30 minutes be spray-dried, obtain modified carbon nano-tube；
（2）By in the hydrochloric acid solution that the 100-110 times of 1mol/L for measuring is added in palygorskite, aniline is added dropwise, with 500-600 rev/min
Stirring 30-40 minutes, under condition of ice bath, ammonium persulfate is slowly added dropwise, 0-5 DEG C of temperature control, stirring reaction 8-9 hour, suction filtration spends
Ion water washing 2-3 time, by product in 60 times vacuum drying, obtains palygorskite polyaniline composite material；
（3）By step（2）The palygorskite polyaniline composite material for obtaining is dissolved in the chloroform of 100 times of amounts, adds DL camphor
Sulfonic acid, 12-14 hours are stirred under room temperature with 300-400 rev/min of speed, are subsequently adding step（1）The product for obtaining, ultrasound point
Remaining residual components is added after scattered 20-30 minutes, continues to stir 10-12 hours with 300-400 rev/min of speed, obtain spinning
Liquid；
（4）Spinning solution is drawn in syringe and spinning solution is collected on collector metallic nickel using electrostatic spinning technique, control
Spinning solution flow processed is 0.2-0.3ml/h, and voltage is 15-20kV, and spinning distance is 8-14cm, and spinning process 5-6 hour is formed
Composite fibre electrode material with certain thickness network structure.
It is an advantage of the invention that：The present invention carries out first the method for high temperature graphitization process to reach purifying to CNT
Effect, simultaneously metallic catalyst evaporates graphited, and CNT will not be destroyed, while degree of crystallinity and leading
Electrically improve；Then the CNT after graphitization, polyaniline, polyethylene glycol oxide etc. net has been made into using electrostatic spinning technique
The composite cellulosic membrane of network structure, causes the fiber of preparation thinner by controlling spinning distance, spinning flow etc., enhances it and compares table
Area, so that electrolyte ion diffusional resistance diminishes, charge transferring channel is more unobstructed, thus shows more preferable capacitive character
Can, specific capacitance is improve, and good cyclical stability is shown using ultracapacitor made by this electrode material, while
Process is simple, is easy to Industry Control.
Palygorskite and aniline are carried out in-situ polymerization by the present invention, because palygorskite has good absorption property and big ratio
Surface area, in being polymerized in the original location, can improve the dispersiveness of polyaniline, to improve the contact area of polyaniline and electrolyte, increase
The utilization rate of big polyaniline, so as to improve specific capacitance；Electrostatic spinning fiber film of the present invention has excellent distribution of pores, this structure
Good passage can be provided for the diffusion of electrolyte ion, with good specific capacitance, with super electricity made by this electrode material
Container electrochemical performance.
Specific embodiment
A kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, by following weight portion（Kilogram）Raw material
Make：Multi-walled carbon nano-tubes 10, lauryl sodium sulfate 1.5, appropriate deionized water, appropriate absolute ethyl alcohol, appropriate chloroform, polyoxy
Change ethene 14, DL camphorsulfonic acid 12, palygorskite 0.2,1mol/L hydrochloric acid solution is appropriate, aniline 10, ammonium persulfate 12.6.
A kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, prepared by following concrete grammar and
Into：
（1）Multi-walled carbon nano-tubes is placed on into graphite crucible stove, in being placed in graphitizing furnace, it is vacuumized, with 10 DEG C/min
2800 DEG C are warming up to, 20 hours are incubated, natural cooling obtains graphitized carbon nano pipe；Above-mentioned graphitized carbon nano pipe is put into
With the speed ball milling 90 minutes of 200 turns/part in ball mill, addition is dissolved in the lauryl sodium sulfate of the deionized waters of 25 times of amounts,
Ultrasound is spray-dried after 20 minutes, obtains modified carbon nano-tube；
（2）By in the hydrochloric acid solution that the 1mol/L of 100 times of amounts is added in palygorskite, aniline is added dropwise, with 500 revs/min 30 points are stirred
Clock, under condition of ice bath, is slowly added dropwise ammonium persulfate, and 0 DEG C of temperature control, stirring reaction 8 hours, suction filtration is washed with deionized 2 times,
By product in 60 times vacuum drying, palygorskite polyaniline composite material is obtained；
（3）By step（2）The palygorskite polyaniline composite material for obtaining is dissolved in the chloroform of 100 times of amounts, adds DL camphor
Sulfonic acid, is stirred 12 hours under room temperature with 300 revs/min of speed, is subsequently adding step（1）The product for obtaining, 20 points of ultrasonic disperse
Remaining residual components is added after clock, continues to be stirred 10 hours with 300 revs/min of speed, obtain spinning solution；
（4）Spinning solution is drawn in syringe and spinning solution is collected on collector metallic nickel using electrostatic spinning technique, control
Spinning solution flow processed is 0.2ml/h, and voltage is 15kV, and spinning distance is 8cm, and spinning process 5 hours is formed and has certain thickness
Network structure composite fibre electrode material.
Teflon septum is immersed in polyvinyl alcohol-sulfogel electrolyte, keep 20 minutes, after taking-up
Under room temperature natural evaporation be dried, then using made by the embodiment collect composite cellulosic membrane metallic nickel as electrode material with
Polyvinyl alcohol-sulfuric acid barrier film is stacked together by sandwich structure, and it is packaged with polyester film, obtains super capacitor
Device.Cyclic voltamogram curve when sweep speed is 5 mV s -1, potential region -0.8-0.2 V obtains super capacitor
The specific capacitance of device is 97 F/g, and specific capacitance remains to be remained above 90% after 1 000 cycle charge discharge electrical testings.
Claims (2)
1. a kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, it is characterised in that by following weight portion
Raw material is made：Multi-walled carbon nano-tubes 10-12, lauryl sodium sulfate 1.5-1.6, appropriate deionized water, appropriate absolute ethyl alcohol, chlorine
Imitative appropriate, polyethylene glycol oxide 14-15, DL camphorsulfonic acid 12-13, palygorskite 0.2-0.3,1mol/L hydrochloric acid solution it is appropriate,
Aniline 10-12, ammonium persulfate 12.6-1.3.
2. a kind of nanometer palygorskite modified polyaniline carbon nano-tube combination electrode material, its feature according to claims 1
It is to be prepared from by following concrete grammar：
（1）Multi-walled carbon nano-tubes is placed on into graphite crucible stove, in being placed in graphitizing furnace, it is vacuumized, with 10-15 DEG C/
Min is warming up to 2800 DEG C, is incubated 20-20 hours, and natural cooling obtains graphitized carbon nano pipe；By above-mentioned graphitized carbon nano
Pipe was put in ball mill with the speed ball milling 90-120 minutes of 200-300 turn/part, and addition is dissolved in the 25-30 times of deionized water measured
Lauryl sodium sulfate, after ultrasonic 20-30 minutes be spray-dried, obtain modified carbon nano-tube；
（2）By in the hydrochloric acid solution that the 100-110 times of 1mol/L for measuring is added in palygorskite, aniline is added dropwise, with 500-600 rev/min
Stirring 30-40 minutes, under condition of ice bath, ammonium persulfate is slowly added dropwise, 0-5 DEG C of temperature control, stirring reaction 8-9 hour, suction filtration spends
Ion water washing 2-3 time, by product in 60 times vacuum drying, obtains palygorskite polyaniline composite material；
（3）By step（2）The palygorskite polyaniline composite material for obtaining is dissolved in the chloroform of 100 times of amounts, adds DL camphor
Sulfonic acid, 12-14 hours are stirred under room temperature with 300-400 rev/min of speed, are subsequently adding step（1）The product for obtaining, ultrasound point
Remaining residual components is added after scattered 20-30 minutes, continues to stir 10-12 hours with 300-400 rev/min of speed, obtain spinning
Liquid；
（4）Spinning solution is drawn in syringe and spinning solution is collected on collector metallic nickel using electrostatic spinning technique, control
Spinning solution flow processed is 0.2-0.3ml/h, and voltage is 15-20kV, and spinning distance is 8-14cm, and spinning process 5-6 hour is formed
Composite fibre electrode material with certain thickness network structure.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707326A (en) * | 2019-04-10 | 2020-01-17 | 中南大学 | Water-system battery current collector, positive electrode, flexible battery, preparation and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130431A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院金属研究所 | Method for purifying nano carbon fiber of multi-wall carbon nano-tube |
-
2016
- 2016-10-31 CN CN201610929776.0A patent/CN106571236A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130431A (en) * | 2006-08-23 | 2008-02-27 | 中国科学院金属研究所 | Method for purifying nano carbon fiber of multi-wall carbon nano-tube |
Non-Patent Citations (3)
| Title |
|---|
| 代涛娟 等: ""纳米结构坡缕石改性聚苯胺超级电容器电极材料的研究"", 《武汉理工大学学报》 * |
| 庞志鹏 等: ""碳纳米管导电纸的制备及改性研究"", 《功能材料》 * |
| 梁军生 等: ""静电纺丝PANI/CNT/PEO超级电容器电极的性能研究"", 《电子元件与材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707326A (en) * | 2019-04-10 | 2020-01-17 | 中南大学 | Water-system battery current collector, positive electrode, flexible battery, preparation and application thereof |
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Application publication date: 20170419 |