CN105506784A - Preparation method of composite carbon nanofibers with high specific surface area - Google Patents

Preparation method of composite carbon nanofibers with high specific surface area Download PDF

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CN105506784A
CN105506784A CN201610081203.7A CN201610081203A CN105506784A CN 105506784 A CN105506784 A CN 105506784A CN 201610081203 A CN201610081203 A CN 201610081203A CN 105506784 A CN105506784 A CN 105506784A
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preparation
pan
spinning
carbon fiber
activated carbon
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贾哲华
贾成浩
赵有华
董斌
徐继任
陶翠
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Yangzhou University
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Yangzhou University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • 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
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • 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
    • H01G11/40—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

Abstract

A preparation method of composite carbon nanofibers with a high specific surface area relates to the technical field of preparation of electrode materials of super capacitors, and comprises the following steps: mixing cellulose acetate and polyacrylonitrile to obtain a spinning solution; carrying out electrospinning to obtain CA/PAN precursors; pre-oxidazing the CA/PAN precursors; carrying out carbonization and actification to obtain CA/PAN activated carbon fibers; mixing the CA/PAN activated carbon fibers with acetylene black, PTFE and ethanol to obtain a mixture; putting the mixture into an oven; drying the mixture into paste; smearing the paste on nickel foam; carrying out drying and tabletting to obtain the CA/PAN composite carbon fiber electrode material. As cellulose acetate contains a large quantity of oxygen-containing groups, and has double functions of pore-forming and chemical surface modification, the hole structure, the specific capacitance and the specific surface area are greatly improved.

Description

A kind of preparation method of compound Nano carbon fiber of high-ratio surface
Technical field
The present invention relates to the preparing technical field of the electrode material of ultracapacitor.
Technical background
Ultracapacitor is a kind of novel energy-storing element between traditional capacitor and electrochmical power source, according to energy storage mechnism, can be divided into electric double layer and fake capacitance two type.The operation principle of electric double layer core is under certain electric field, and electrode plate surface can form charge layer closely, i.e. an electric double layer due to the displacement of electric charge, thus produces capacity effect; And the number of the electricity of this charge layer (ratio capacitance) first depends on the size of the specific area of electrode material.
Material with carbon element is owing to having abundant duct, and higher specific area and be widely used as the electrode material of double layer capacitor, conventional material with carbon element comprises granular activated carbon, activated carbon fiber, carbon aerogels, CNT etc.Wherein, activated carbon fiber uniqueness unidimensional scale effect thus be provided with extremely excellent mass-transfer performance; And high temperature carbonization, activation (graphitization) make it have good electric conductivity fully.Therefore, activated carbon fiber is especially suitable as the electrode material of ultracapacitor.The preparation method of activated carbon fiber mainly comprises wet spinning, melt spinning and electrostatic spinning.Wherein, electrostatic spinning can obtain the fibrous material of micro/nano-scale, thus on mass transfer and electric conductivity, has more advantage.The presoma high polymer that electrostatic spinning is conventional mainly comprises polyacrylonitrile, polyimides, polyvinyl alcohol, polyvinylpyrrolidone, polystyrene, shitosan, cellulose acetate etc.Because the carbonisation of different polymer is different, by carrying out rational proportion to two kinds of polymer, different pore-size distributions and specific area can be createed, the activated carbon fiber of abundant pore structure.If the patent No. is, in the patent of invention of 201510176445.X, polyacrylonitrile is carried out electrostatic spinning according to certain mass than mixing with polyvinylpyrrolidone, prepare porous carbon nanofiber through pre-oxidation and carbonization, specific area is 489m 2/ g.
Containing more oxy radical in cellulose acetate, cellulose acetate is cellulosic derivative simultaneously, and cellulose has abundance, renewable, environmental protection, the features such as cost of material is cheap, so receive increasing concern, itself and other polymer is carried out compound thus reaches the object of modification.If the patent No. is, in the patent of invention of 201510079823.2, CA and PAN is carried out compound according to different quality ratio, use wet spinning to obtain vinegar nitrile fiber, this fiber improves the defect that acrylic fiber hygroscopicity is poor, easily play electrostatic; Improve the shortcoming that acetate fiber intensity is low, taking is poor.Zhou Ming (the New Chemical Materials of Southern Yangtze University, 2011,39(3): 76-78) CA and PAN is mixed and made into spinning liquid as precursor, and carries out electrostatic spinning, obtain CA/PAN composite cellulosic membrane, the mass ratio having investigated CA and PAN is on the impact of the mechanical property of composite nano fiber and bacteriological filtration performance.Although report CA and PAN in document to carry out compound and electrostatic spinning prepares composite cellulosic membrane, have no to heat-treat it and prepare activated carbon fiber and the report being applied to electrode material for super capacitor.
Summary of the invention
The object of the present invention is to provide a kind of preparation method overcoming the preparation method of the high-ratio surface CA/PAN carbon fiber reinforce plastic electrode material for ultracapacitor of prior art defect,
The present invention includes following steps:
1) cellulose acetate (CA) and polyacrylonitrile (PAN) are mixed to form spinning solution;
2) spinning solution is carried out electrostatic spinning, obtain CA/PAN precursor;
3) by after CA/PAN precursor pre-oxidation, carbonization, activation, CA/PAN activated carbon fiber is obtained;
4) mixing of CA/PAN activated carbon fiber, acetylene black, PTFE and ethanol be placed in baking oven and bake pasty state, then spread upon in nickel foam, compressing tablet after drying, obtains CA/PAN carbon fiber reinforce plastic electrode material.
Containing more oxy radical in cellulose acetate of the present invention (CA), there is pore-creating and improve the dual-use function of material surface chemistries, the present invention obtains the CA/PAN activated carbon fiber of high-specific surface area and good electrical chemical property through pre-oxidation, carbonization and activation process, and then by the CA/PAN activated carbon fiber after pre-oxidation, carbonization, activation for the manufacture of electrode material, greatly improve pore structure, ratio capacitance and specific area.
The advantage that the present invention has and good effect are:
1.the present invention regulates pore-size distribution and the specific area of active nano carbon fiber by the mass ratio of control CA and PAN, thus realizes the controlled synthesis to micro/nano-scale activated carbon fiber.
2.containing more oxy radical in cellulose acetate, make it in this preparation method, have dual-use function, namely realize pore-creating and surface chemical modification simultaneously, thus simplify the preparation technology of porous carbon fiber.
3.cellulose acetate is as the derivative of native cellulose, and abundance is a kind of renewable resource.
Further, cellulose acetate of the present invention is 100: 1 ~ 1: 100 with the mixing quality ratio of polyacrylonitrile.Cellulose acetate has the dual-use function of pore-creating and surface chemical modification, and itself and polyacrylonitrile are mixed with activated carbon fiber in proportion, can reach the effect of increasing specific surface area and chemical property.
Described step 1) cellulose acetate and polyacrylonitrile is mixed under 60 DEG C of water-baths, magnetic agitation, after leaving standstill, form spinning solution.60 DEG C of water-baths can be accelerated the dissolving of CA and PAN with stirring and fully mix.
Described step 2) in, environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage is 16 ~ 21kV, and spinning speed is 0.1 ~ 0.5mm/min, and spinning distance is 15 ~ 20cm.The control of temperature and humidity contributes to the volatilization of solvent in spinning process, is convenient to into silk, and the fiber precursor even size distribution obtained under this condition, diameter is less.
In described step 3), described pre-oxidation carries out under air atmosphere, and Pre oxidation is 250 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 2h.Fiber precursor makes macromolecule be converted into resistant to elevated temperatures trapezium structure through cyclodehydrogenation in preoxidation process, to keep original fiber morphology under high temperature cabonization.Make fiber precursor can obtain sufficient pre-oxidation under this condition.
In described step 3), described carbonization carries out under nitrogen atmosphere, and carburizing temperature is 800 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 2h.The object of carbonization is the non-carbon in removing fiber, generates the carbon fiber that phosphorus content is high.Fiber can be made under this condition to obtain sufficient carbonization.
In described step 3), described activation is: be placed in by the material after carbonization after the KOH aqueous solution floods 2h, dry at 150 DEG C, under being placed in nitrogen atmosphere again, be that 10 DEG C/min is warming up to 800 DEG C with heating rate, insulation 0.5h is finally the HCl aqueous solution and the deionized water washing post-drying of 5% with mass fraction.The object of activation is in order to further reaming, increases the specific area of material.The specific area of the activated carbon fiber obtained under this condition is relatively the highest.
Accompanying drawing explanation
Fig. 1 is the N of the activated carbon fiber obtained in example 1,2,3,4,5 2adsorption desorption isothermal curve.
Fig. 2 is the constant current charge-discharge curve of electrode material under the current density of 1A/g obtained in example 1,2,3,4,5.
Fig. 3 is the curve of ratio capacitance with current density change of the electrode material obtained in example 1,2,3,4,5.
Detailed description of the invention
One, electrode material is prepared:
1, example 1:
Electrostatic spinning: take 3g cellulose acetate and be placed in conical flask, adds the DMF(dimethyl formamide of 27g), after 60 DEG C of lower magnetic forces stir 4h, leave standstill 1h, the spinning solution that homogeneous, transparent mass fraction is 10% can be obtained.Environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage: 16kV, spinning speed: 0.1mm/min, spinning distance: 16cm.
Pre-oxidation: under air atmosphere, Pre oxidation is 250 DEG C, and heating rate is 1 DEG C/min, temperature retention time 2h; Carbonization: under blanket of nitrogen, carburizing temperature is 800 DEG C, and heating rate is 1 DEG C/min, temperature retention time 2h; Activation: activator is potassium hydroxide, the mass ratio of potassium hydroxide and carbon fiber is 3/4, be mixed with the KOH solution of 1wt% by impregnated carbon fiber wherein 2h, then dry at 150 DEG C, under blanket of nitrogen, activation temperature is 800 DEG C, heating rate is 10 DEG C/min, temperature retention time 0.5h, the HCl solution of finally use 5% and deionized water successively repeatedly rinse to be placed in baking oven dries, and obtains activated carbon nanofiber.
The preparation of electrode: be that 85:10:5 mixes with PTFE according to mass ratio by activated carbon fiber, acetylene black, add ethanol, stir 6h, ultrasonic half an hour, then be placed in 60 DEG C, baking oven and bake pasty state, it is spread upon in nickel foam uniformly, dry 4 ~ 5h in baking oven, taking-up is placed on 10MPa lower sheeting on tablet press machine, obtains pellet electrode material.
2, example 2:
Electrostatic spinning: take 2.4g cellulose acetate and 0.6gPAN(polyacrylonitrile) be placed in conical flask, add the DMF of 27g, after 60 DEG C of lower magnetic forces stir 4h, leave standstill 1h, the spinning solution that homogeneous, transparent mass fraction is 10% can be obtained.Environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage: 18kV, spinning speed: 0.2mm/min, spinning distance: 17cm.
Pre-oxidation: under air atmosphere, Pre oxidation is 250 DEG C, and heating rate is 2 DEG C/min, temperature retention time 2h; Carbonization: under blanket of nitrogen, carburizing temperature is 800 DEG C, and heating rate is 2 DEG C/min, temperature retention time 2h; Activation: activator is potassium hydroxide, the mass ratio of potassium hydroxide and carbon fiber is 3/4, be mixed with the KOH solution of 1wt% by impregnated carbon fiber wherein 2h, then dry at 150 DEG C, under blanket of nitrogen, activation temperature is 800 DEG C, heating rate is 10 DEG C/min, temperature retention time 0.5h, the HCl solution of finally use 5% and deionized water successively repeatedly rinse to be placed in baking oven dries, and obtains activated carbon nanofiber.
The preparation of electrode: be that 85:10:5 mixes with PTFE according to mass ratio by activated carbon fiber, acetylene black, adds ethanol, stirs 6h, ultrasonic half an hour, then be placed in 60 DEG C, baking oven and bake pasty state, it spread upon in the nickel foam handled well uniformly, application area is 1 × 1cm -1, take out after putting into oven drying 4 ~ 5h and be placed on 10MPa lower sheeting on tablet press machine, obtain pellet electrode material.
3, example 3:
Electrostatic spinning: take 1.8g cellulose acetate and 1.2g polyacrylonitrile is placed in conical flask, adds the DMF of 27g, leaves standstill 1h, can obtain the spinning solution that homogeneous, transparent mass fraction is 10% after 60 DEG C of lower magnetic forces stir 4h.Environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage: 19kV, spinning speed: 0.3mm/min, spinning distance: 18cm.
Pre-oxidation: under air atmosphere, Pre oxidation is 250 DEG C, and heating rate is 3 DEG C/min, temperature retention time 2h; Carbonization: under blanket of nitrogen, carburizing temperature is 800 DEG C, and heating rate is 3 DEG C/min, temperature retention time 2h; Activation: activator is potassium hydroxide, the mass ratio of potassium hydroxide and carbon fiber is 3/4, be mixed with the KOH solution of 1wt% by impregnated carbon fiber wherein 2h, then dry at 150 DEG C, under blanket of nitrogen, activation temperature is 800 DEG C, heating rate is 10 DEG C/min, temperature retention time 0.5h, the HCl solution of finally use 5% and deionized water successively repeatedly rinse to be placed in baking oven dries, and obtains activated carbon nanofiber.
The preparation of electrode: be that 85:10:5 mixes with PTFE according to mass ratio by activated carbon fiber, acetylene black, add ethanol, stir 6h, ultrasonic half an hour, then be placed in 60 DEG C, baking oven and bake pasty state, it is spread upon in nickel foam uniformly, dry 4 ~ 5h in baking oven, taking-up is placed on 10MPa lower sheeting on tablet press machine, obtains pellet electrode material.
4, example 4:
Electrostatic spinning: take 0.6g cellulose acetate and 2.4g polyacrylonitrile is placed in conical flask, adds the DMF of 27g, leaves standstill 1h, can obtain the spinning solution that homogeneous, transparent mass fraction is 10% after 60 DEG C of lower magnetic forces stir 4h.Environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage: 20kV, spinning speed: 0.4mm/min, spinning distance: 19cm.
Pre-oxidation: under air atmosphere, Pre oxidation is 250 DEG C, and heating rate is 4 DEG C/min, temperature retention time 2h; Carbonization: under blanket of nitrogen, carburizing temperature is 800 DEG C, and heating rate is 4 DEG C/min, temperature retention time 2h; Activation: activator is potassium hydroxide, the mass ratio of potassium hydroxide and carbon fiber is 3/4, be mixed with the KOH solution of 1wt% by impregnated carbon fiber wherein 2h, then dry at 150 DEG C, under blanket of nitrogen, activation temperature is 800 DEG C, heating rate is 10 DEG C/min, temperature retention time 0.5h, the HCl solution of finally use 5% and deionized water successively repeatedly rinse to be placed in baking oven dries, and obtains activated carbon nanofiber.
The preparation of electrode: be that 85:10:5 mixes with PTFE according to mass ratio by activated carbon fiber, acetylene black, add ethanol, stir 6h, ultrasonic half an hour, then be placed in 60 DEG C, baking oven and bake pasty state, it is spread upon in nickel foam uniformly, dry 4 ~ 5h in baking oven, taking-up is placed on 10MPa lower sheeting on tablet press machine, obtains pellet electrode material.
5, example 5:
Electrostatic spinning: take 3g polyacrylonitrile and be placed in conical flask, add the DMF of 27g, leaves standstill 1h, can obtain the spinning solution that homogeneous, transparent mass fraction is 10% after 60 DEG C of lower magnetic forces stir 4h.Environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage: 21kV, spinning speed: 0.5mm/min, spinning distance: 20cm.
Pre-oxidation: under air atmosphere, Pre oxidation is 250 DEG C, and heating rate is 5 DEG C/min, temperature retention time 2h; Carbonization: under blanket of nitrogen, carburizing temperature is 800 DEG C, and heating rate is 5 DEG C/min, temperature retention time 2h; Activation: activator is potassium hydroxide, the mass ratio of potassium hydroxide and carbon fiber is 3/4, be mixed with the KOH solution of 1wt% by impregnated carbon fiber wherein 2h, then dry at 150 DEG C, under blanket of nitrogen, activation temperature is 800 DEG C, heating rate is 10 DEG C/min, temperature retention time 0.5h, the HCl solution of finally use 5% and deionized water successively repeatedly rinse to be placed in baking oven dries, and obtains activated carbon nanofiber.
The preparation of electrode: be that 85:10:5 mixes with PTFE according to mass ratio by activated carbon fiber, acetylene black, add ethanol, stir 6h, ultrasonic half an hour, then be placed in 60 DEG C, baking oven and bake pasty state, it is spread upon in nickel foam uniformly, dry 4 ~ 5h in baking oven, taking-up is placed on 10MPa lower sheeting on tablet press machine, obtains pellet electrode material.
Two, the test of the chemical property of each electrode material and result:
The test of chemical property: adopt three-electrode system, the electrode obtained with above-mentioned each example is for working electrode, platinum plate electrode is to electrode, saturated calomel electrode is reference electrode, and the KOH aqueous solution of 6M is electrolyte, and test voltage scope is-0.6 ~ 0.2V, carry out cyclic voltammetric and constant current charge-discharge test, test when current density is 1A/g, the ratio capacitance of each electrode material, see the following form:
As seen from the above table: the activated carbon fiber that the specific area of the activated carbon fiber prepared after cellulose acetate (CA) and polyacrylonitrile (PAN) being mixed in proportion is obtained relative to simple CA and PAN is enhanced, and its chemical property as the electrode material of ultracapacitor also has larger lifting.As can be seen here, CA adds the specific area increasing activated carbon fiber, serves the effect of pore-creating and surface chemical modification wherein.
Three, the description of the drawings:
Fig. 1 is sample N 2adsorption desorption isothermal curve.Due to the effect of capillary condensation, adsorption isotherm and desorption isotherm are not overlapped, occurs delayed winding, show that sample all has certain middle pore property; Simultaneously under lower relative pressure, owing to there is micropore filling, nitrogen adsorption amount is increased sharply, show that sample also has certain microporous properties.
Fig. 2 is the constant current charge-discharge curve map of sample when current density is 1A/g.Curve is that near symmetrical is triangular shaped, has excellent electrochemical reversibility and charge-discharge performance.
Fig. 3 is the relation of sample current density and ratio capacitance.Along with the increase of current density, charging completes within a short period of time, ion moves to electrode surface from solution does not have time enough to enter in the less hole of electrode interior, and some material with carbon element specific area is not used effectively, and thus can cause the decay of capacitance.

Claims (7)

1. a preparation method for the compound Nano carbon fiber of high-ratio surface, is characterized in that comprising the following steps:
1) cellulose acetate and polyacrylonitrile are mixed to form spinning solution;
2) spinning solution is carried out electrostatic spinning, obtain CA/PAN precursor;
3) by after CA/PAN precursor pre-oxidation, carbonization, activation, CA/PAN activated carbon fiber is obtained;
4) mixing of CA/PAN activated carbon fiber, acetylene black, PTFE and ethanol be placed in baking oven and bake pasty state, then spread upon in nickel foam, compressing tablet after drying, obtains CA/PAN carbon fiber reinforce plastic electrode material.
2. preparation method according to claim 1, is characterized in that: described cellulose acetate is 100: 1 ~ 1: 100 with the mixing quality ratio of polyacrylonitrile.
3. preparation method according to claim 1 or 2, is characterized in that: described step 1) cellulose acetate and polyacrylonitrile is mixed under 60 DEG C of water-baths, magnetic agitation, after leaving standstill, form spinning solution.
4. preparation method according to claim 1, is characterized in that: described step 2) in, environment temperature≤40 DEG C of electrostatic spinning, humidity≤30%, spinning voltage is 16 ~ 21kV, and spinning speed is 0.1 ~ 0.5mm/min, and spinning distance is 15 ~ 20cm.
5. preparation method according to claim 1, it is characterized in that: in described step 3), described pre-oxidation carries out under air atmosphere, and Pre oxidation is 250 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 2h.
6. preparation method according to claim 1, it is characterized in that: in described step 3), described carbonization carries out under nitrogen atmosphere, and carburizing temperature is 800 DEG C, and heating rate is 1 ~ 5 DEG C/min, and temperature retention time is 2h.
7. preparation method according to claim 1, it is characterized in that: in described step 3), described activation is: be placed in by the material after carbonization after the KOH aqueous solution floods 2h, dry at 150 DEG C, under being placed in nitrogen atmosphere again, be that 10 DEG C/min is warming up to 800 DEG C with heating rate, insulation 0.5h is finally the HCl aqueous solution and the deionized water washing post-drying of 5% with mass fraction.
CN201610081203.7A 2016-02-05 2016-02-05 Preparation method of composite carbon nanofibers with high specific surface area Pending CN105506784A (en)

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CN111058126A (en) * 2019-11-21 2020-04-24 宁波工程学院 Preparation method of porous hollow carbon nanofiber and supercapacitor containing porous hollow carbon nanofiber
CN112279304A (en) * 2020-08-26 2021-01-29 甘肃农业职业技术学院 Fe3O4Porous carbon nanofiber and preparation method and application thereof
CN112342644A (en) * 2020-11-26 2021-02-09 湖北亿纬动力有限公司 Porous carbon fiber and preparation method and application thereof
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CN105869925A (en) * 2016-05-10 2016-08-17 扬州大学 Preparation method of nitrogen-doped CA/PAN-based carbon microsphere electrode material
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CN112745522A (en) * 2020-02-06 2021-05-04 北京化工大学 Preparation method of surface-modified electrostatic spinning aerogel, obtained aerogel and application
CN112279304A (en) * 2020-08-26 2021-01-29 甘肃农业职业技术学院 Fe3O4Porous carbon nanofiber and preparation method and application thereof
CN112342644A (en) * 2020-11-26 2021-02-09 湖北亿纬动力有限公司 Porous carbon fiber and preparation method and application thereof
CN114823155A (en) * 2022-04-01 2022-07-29 北京理工大学 Three-dimensional conductive material and preparation method and application thereof

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