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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- preparation
- pan
- spinning
- carbon fiber
- activated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000002134 carbon nanofiber Substances 0.000 title abstract 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 43
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 40
- 238000009987 spinning Methods 0.000 claims abstract description 35
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000006230 acetylene black Substances 0.000 claims abstract description 8
- 239000006260 foam Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000010041 electrostatic spinning Methods 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 230000014759 maintenance of location Effects 0.000 claims description 19
- 238000001994 activation Methods 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000005255 carburizing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 235000011837 pasties Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000001523 electrospinning Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000012190 activator Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007385 chemical modification Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000826860 Trapezium Species 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- 230000000721 bacterilogical effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002133 porous carbon nanofiber Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- -1 shitosan Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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, 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
- H01G11/24—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, 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
- H01G11/26—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, 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)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610081203.7A CN105506784A (en) | 2016-02-05 | 2016-02-05 | Preparation method of composite carbon nanofibers with high specific surface area |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610081203.7A CN105506784A (en) | 2016-02-05 | 2016-02-05 | Preparation method of composite carbon nanofibers with high specific surface area |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105506784A true CN105506784A (en) | 2016-04-20 |
Family
ID=55715072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610081203.7A Pending CN105506784A (en) | 2016-02-05 | 2016-02-05 | Preparation method of composite carbon nanofibers with high specific surface area |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105506784A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105761950A (en) * | 2016-05-10 | 2016-07-13 | 扬州大学 | Preparation method of porous nitrogen-rich carbon fiber electrode |
| CN105869927A (en) * | 2016-06-28 | 2016-08-17 | 扬州大学 | Method for preparing high-specific-surface-area and high-specific-capacitance carbon fibers by random copolymers |
| CN105869925A (en) * | 2016-05-10 | 2016-08-17 | 扬州大学 | Preparation method of nitrogen-doped CA/PAN-based carbon microsphere electrode material |
| CN106098413A (en) * | 2016-07-12 | 2016-11-09 | 扬州大学 | A kind of preparation method of flexible super capacitor electrode material |
| CN106169380A (en) * | 2016-07-26 | 2016-11-30 | 东华大学 | A kind of preparation method of flexible self-supporting carbon electrode material |
| CN106192212A (en) * | 2016-07-03 | 2016-12-07 | 郑州轻工业学院 | A kind of preparation method of nano-cellulose based carbon fiber mesh non-woven fabrics flexible electrode |
| CN106929948A (en) * | 2017-01-19 | 2017-07-07 | 湖北大学 | A kind of titanium oxide meso-porous nano fiber producing processes and its application based on coaxial electrostatic spinning |
| WO2019029101A1 (en) * | 2017-08-11 | 2019-02-14 | 南通金康弘纺织品有限公司 | Preparation method for activated carbon fiber |
| CN110127658A (en) * | 2019-07-01 | 2019-08-16 | 青海民族大学 | A kind of supercapacitor mesoporous carbon nanometer combined electrode material and preparation method thereof |
| CN110295437A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of home textile fabric using vinegar blueness fiber |
| 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 |
| 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 |
| CN114823155A (en) * | 2022-04-01 | 2022-07-29 | 北京理工大学 | Three-dimensional conductive material and preparation method and application thereof |
| CN116219584A (en) * | 2023-03-07 | 2023-06-06 | 北华大学 | Method for preparing hollow carbon nanofiber by using uniaxial electrostatic spinning technology and application of hollow carbon nanofiber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280640A (en) * | 2011-07-12 | 2011-12-14 | 南开大学 | Novel anode material for lithium-ion secondary battery |
| CN103943378A (en) * | 2013-01-21 | 2014-07-23 | 东莞市长安东阳光铝业研发有限公司 | Manufacturing method of electrode used for supercapacitor |
| CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
-
2016
- 2016-02-05 CN CN201610081203.7A patent/CN105506784A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102280640A (en) * | 2011-07-12 | 2011-12-14 | 南开大学 | Novel anode material for lithium-ion secondary battery |
| CN103943378A (en) * | 2013-01-21 | 2014-07-23 | 东莞市长安东阳光铝业研发有限公司 | Manufacturing method of electrode used for supercapacitor |
| CN104805535A (en) * | 2015-04-14 | 2015-07-29 | 华南理工大学 | Preparation method of porous carbon nanofiber |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105761950B (en) * | 2016-05-10 | 2018-01-30 | 扬州大学 | A kind of preparation method of porous rich nitrogen carbon fiber electrode |
| CN105869925A (en) * | 2016-05-10 | 2016-08-17 | 扬州大学 | Preparation method of nitrogen-doped CA/PAN-based carbon microsphere electrode material |
| CN105761950A (en) * | 2016-05-10 | 2016-07-13 | 扬州大学 | Preparation method of porous nitrogen-rich carbon fiber electrode |
| CN105869925B (en) * | 2016-05-10 | 2018-01-30 | 扬州大学 | A kind of preparation method of N doping CA/PAN bases carbosphere electrode material |
| CN105869927A (en) * | 2016-06-28 | 2016-08-17 | 扬州大学 | Method for preparing high-specific-surface-area and high-specific-capacitance carbon fibers by random copolymers |
| CN105869927B (en) * | 2016-06-28 | 2018-05-08 | 扬州大学 | A kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber |
| CN106192212B (en) * | 2016-07-03 | 2018-07-31 | 郑州轻工业学院 | A kind of preparation method of nano-cellulose based carbon fiber mesh non-woven fabrics flexible electrode |
| CN106192212A (en) * | 2016-07-03 | 2016-12-07 | 郑州轻工业学院 | A kind of preparation method of nano-cellulose based carbon fiber mesh non-woven fabrics flexible electrode |
| CN106098413A (en) * | 2016-07-12 | 2016-11-09 | 扬州大学 | A kind of preparation method of flexible super capacitor electrode material |
| CN106098413B (en) * | 2016-07-12 | 2018-07-31 | 扬州大学 | A kind of preparation method of flexible super capacitor electrode material |
| CN106169380A (en) * | 2016-07-26 | 2016-11-30 | 东华大学 | A kind of preparation method of flexible self-supporting carbon electrode material |
| CN106929948A (en) * | 2017-01-19 | 2017-07-07 | 湖北大学 | A kind of titanium oxide meso-porous nano fiber producing processes and its application based on coaxial electrostatic spinning |
| WO2019029101A1 (en) * | 2017-08-11 | 2019-02-14 | 南通金康弘纺织品有限公司 | Preparation method for activated carbon fiber |
| CN110295437A (en) * | 2018-03-23 | 2019-10-01 | 上海水星家用纺织品股份有限公司 | A kind of home textile fabric using vinegar blueness fiber |
| CN110127658A (en) * | 2019-07-01 | 2019-08-16 | 青海民族大学 | A kind of supercapacitor mesoporous carbon nanometer combined electrode material and preparation method thereof |
| 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 |
| 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 |
| CN116219584A (en) * | 2023-03-07 | 2023-06-06 | 北华大学 | Method for preparing hollow carbon nanofiber by using uniaxial electrostatic spinning technology and application of hollow carbon nanofiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105506784A (en) | Preparation method of composite carbon nanofibers with high specific surface area | |
| CN104392847B (en) | Preparation method of morphology controllable metal oxide/active carbon fiber combination electrode material | |
| CN106848314B (en) | The lithium-sulfur cell preparation method of double-layer porous carbon nano-fiber and the method for preparing positive electrode using it | |
| CN105761950B (en) | A kind of preparation method of porous rich nitrogen carbon fiber electrode | |
| CN111549449B (en) | Preparation method of lignin-based flexible carbon nanofiber self-supporting electrode material | |
| CN105869925B (en) | A kind of preparation method of N doping CA/PAN bases carbosphere electrode material | |
| CN110136998B (en) | Preparation method and application of metal organic framework carbon fiber composite film | |
| CN106098413B (en) | A kind of preparation method of flexible super capacitor electrode material | |
| Tan et al. | Carbon nanofibers prepared by electrospinning accompanied with phase-separation method for supercapacitors: Effect of thermal treatment temperature | |
| CN104071768B (en) | Part graphitization porous carbon electrode material of aperture fractional distribution and preparation method thereof | |
| CN107188171B (en) | Porous carbon materials and preparation method and the porous carbon-based electrode material for supercapacitor prepared using the porous carbon materials | |
| CN111118883B (en) | Cellulose-based carbon nanofiber composite material and preparation and application thereof | |
| CN109417171A (en) | Classifying porous nano-sized carbon/sulphur composite cathode it is adjustable and can volume production synthesis | |
| CN105671692A (en) | Preparation method of melamine resin modified nitrogen-rich porous carbon fiber electrode material | |
| CN106784745A (en) | The sodium-ion battery method for manufacturing electric spinning of cobaltosic oxide carbon nano-fiber | |
| CN109727781A (en) | A kind of self-supporting flexible super capacitor electrode material and preparation method | |
| CN110331469A (en) | The preparation method and applications of CuO/Cu nitrogen-doped carbon nano-fiber material | |
| CN113201809B (en) | Hierarchical porous carbon-based composite supercapacitor electrode material and preparation method thereof | |
| Sasono et al. | Nanofiber-enrich dispersed activated carbon derived from coconut shell for supercapacitor material | |
| Yan et al. | Heteroatoms in situ-doped hierarchical porous hollow-activated carbons for high-performance supercapacitor | |
| CN108314008A (en) | A kind of full carbon nano-fiber aeroges of flexible, compressible 3D and preparation method thereof | |
| CN109422263A (en) | Cellulose porous activated carbon and preparation method and application thereof | |
| He et al. | Carbon nano-fibers/ribbons with meso/macro pores structures for supercapacitor | |
| CN108455604B (en) | Carboxyl asphalt-based porous carbon and preparation method and application thereof | |
| CN110033953B (en) | Functionalized carbon cloth conductive substrate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160420 |