CN105869927B - A kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber - Google Patents
A kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber Download PDFInfo
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- CN105869927B CN105869927B CN201610479220.6A CN201610479220A CN105869927B CN 105869927 B CN105869927 B CN 105869927B CN 201610479220 A CN201610479220 A CN 201610479220A CN 105869927 B CN105869927 B CN 105869927B
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- Y02E60/13—Energy storage using capacitors
Abstract
A kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber, belong to sustainable energy technology, acrylonitrile acrylic copolymer is dissolved in N, in N dimethylformamides, acrylonitrile acrylic copolymer nanofiber is made by electrospinning process with this spinning solution, pre-oxidized successively again, carbonization treatment, obtain polyacrylonitrile base co-polymer carbon fiber；Polyacrylonitrile base co-polymer carbon fiber is mixed into post activation with KOH aqueous solutions, obtains high-specific surface area and high specific capacitance carbon fiber.The method of the present invention has the advantages that technique is simple, and spinning fibre adjusts, environmentally protective.The ultracapacitor is a kind of energy-storage travelling wave tube between traditional capacitor and battery, has the advantages of power density is big, and energy density is high, and charge/discharge rates are fast, have extended cycle life.
Description
Technical field
The invention belongs to sustainable energy technology, and in particular to the production technical field of ultracapacitor.
Background technology
Electrostatic spinning technique be it is a kind of can rapidly, continuously, simple and effective acquisition nanometer is to several micron order fibers
Method.Spinning fibre has the characteristics that technique is simple, fibre diameter adjusts, high-specific surface area and porosity.Therefore extensively should
For fields such as bioengineered tissue, gas-liquid filtering, sensing materials.During electrostatic spinning, polymer solution or melt exist
Charge accumulated under the action of high voltage electric field, electric field drawing force gradually exceed the surface tension of polymeric liquid, polymer solution spray
Penetrate, stretch and as solvent volatilization or melt cooling are gradually solidified into silk, receiving terminal obtains nanofiber.
Ultracapacitor, is called electrochemical capacitor, is stored up by adion or the reaction of quick surface oxidation reduction
Deposit energy.Ultracapacitor has power density high, has extended cycle life, charge/discharge rates are fast as a kind of novel energy storage apparatus
And the advantages that environmentally protective, it is widely used in the fields such as information technology, electric automobile, space flight and aviation, science and techniques of defence.According to its storage
Can mechanism difference, double layer capacitor can be divided into, Faraday pseudo-capacitance itself and three kinds of hybrid capacitors.Electric double layer capacitance
The electric double layer capacitance that device is mainly formed by electric charge on interface between electrode and electrolyte is come energy storage.Double layer capacitor
Electrode material be usually porous charcoal, by the diffusion of electrolyte, ion forms electric double layer in the duct of electrode material,
Therefore the specific capacitance of double layer capacitor depends on ratio surface and the pore structure of electrode material.Faraday pseudo-capacitance device is main
By the way that redox reaction or the chemisorbed/desorption of Rapid reversible occur in the surface of electrode material or near surface come energy storage,
The characteristics of reaction is that the transfer of electric charge occurs on the surface of electrode or near surface and has non-continuous faradic currents to produce, its
Electrode material is mainly metal oxide, conducting polymer etc..Hybrid capacitors have two kinds of energy storage mechnisms, two electrodes point concurrently
It is not made of fake capacitance class or battery class electrode material and porous charcoal.
The prior art prepare high specific capacitance carbon fiber there are the defects of：Carbon fiber is a kind of activated carbon thing in threadiness
Matter, mainly by carrying out low temperature pre-oxidation to precursor fibre, then obtains in conjunction with high temperature cabonization.At present, carbon fiber is prepared
It is primarily present two problems：1st, under carburizing temperature, the copolymer structure linearly assembled is unstable；2nd, the carbon of most of copolymers
Yield is relatively low.
The content of the invention
The defect existing in the prior art for more than, the present invention seeks to propose that a kind of random copolymer prepares high-ratio surface
The method of product and high specific capacitance carbon fiber.
The present invention comprises the following steps：
1）Acrylonitrile acrylic copolymer P is formed by radical polymerization（AN-co-AA）, by acrylonitrile acrylic acid copolymer
Thing P（AN-co-AA）It is dissolved in n,N-Dimethylformamide, forms spinning solution；By electrospinning process be made acrylonitrile-
Acrylic copolymer nanofiber；
2）Acrylonitrile-acrylic acid copolymer nanofiber is pre-oxidized successively using tube furnace, carbonization treatment, obtained poly-
Acrylonitrile copolymer carbon fiber；
3）Polyacrylonitrile base co-polymer carbon fiber is mixed into post activation with KOH aqueous solutions, obtains high-specific surface area and high than electricity
Hold carbon fiber.
The present invention is by radical polymerization synthesis of acrylonitrile acrylic copolymer, by electrostatic spinning technique, with N, N- bis-
Methylformamide is solvent, is prepared for acrylonitrile-acrylic acid copolymer nanofiber.Research shows：A small amount of acrylic acid copolymer group
The addition divided can improve morphology of carbon fibers, but the addition of a large amount of acrylic acid can cause carbon fiber to shrink aggravation, there is the production of bead string phenomenon
It is raw；The increase of copolymerization component ratio can increase the degree of roughness of fiber surface, and play the role of certain reaming.
Then carbonization treatment is carried out to electrospinning fibre using tube furnace, obtains polyacrylonitrile base co-polymer carbon fiber, and by
Scanning electron microscope and absorption test characterize carbon fiber, the results showed that it is certain that the addition of acrylate make it that carbon fiber has
Shrink, and with the increase of acrylic acid content, shrink even more serious, fiber morphology heterogeneity.
Obtained carbon fiber is mixed with KOH and is activated, activation process is that activator is complicated with being carried out between carbon material
The process of chemical reaction, can be with the specific surface area of controlled material, pore-size distribution and surface heteroatom group.By run-inflation effect,
Dehydration, fragrant condensation and skeleton function ultimately form the carbon material of high-specific surface area.Obtained carbon fiber will be activated
Carry out electro-chemical test, the results showed that effectively obtain the electrode material of high specific capacitance, the application as ultracapacitor.
The method of the present invention has the advantages that technique is simple, and spinning fibre adjusts, environmentally protective.Spinning fibre size is averaged
150~200 nm, 2117 m of carbon fiber specific surface area2·g-1, the specific capacitance of ultracapacitor is up to 300 F g-1.This is super
Capacitor is a kind of energy-storage travelling wave tube between traditional capacitor and battery, has that power density is big, high excellent of energy density
Point, and charge/discharge rates are fast, have extended cycle life, it is environmentally safe.
Further, acrylonitrile acrylic copolymer P of the present invention（AN-co-AA）With N,N-dimethylformamide
Mixing quality ratio is 1: 9.The spinning solution formed with this has suitable viscosity, so that smooth spinning goes out size uniform, does not have
The spinning fibre of a beading.
Voltage is 16 kV during the electrostatic spinning, and the flow velocity of spinning solution is 0.1 mm/min, between spinneret and receiver
Distance be 14 cm.Spinning fibre size uniformity can be obtained, it is ensured that manufactured fiber does not have bead string phenomenon.
The temperature of the pre-oxidation, time conditions are 200~300 DEG C, 120min.During the temperature of the preferable pre-oxidation
Between condition be 240 DEG C.When temperature is 240 DEG C, P（AN-co-AA）Morphology of carbon fibers structure is stablized the most.
The temperature of the carbonization, time conditions are 700~900 DEG C, 120min.The carbon being carbonized under this temperature range is fine
Dimension has certain nitrogen content, and has certain degree of graphitization.The temperature of the preferable carbonization is 800 DEG C, obtained carbon
The electrode material chemical property that fiber does ultracapacitor is best.
The mixing quality ratio of the polyacrylonitrile base co-polymer carbon fiber and KOH is 1: 4.Should under the conditions of activation effect most
It is good, obtain big specific surface area, wide pore-size distribution carbon fiber.
The temperature conditionss of the activation are 700~900 DEG C.Activated under this temperature range, carbon fiber has certain nitrogen
Content, and there is certain degree of graphitization.
Further, the temperature conditionss of the activation are 800 DEG C, are activated at such a temperature, are made by run-inflation effect, dehydration
With the carbon fiber that high-specific surface area is ultimately formed with skeleton function.
Brief description of the drawings
Fig. 1 is the SEM electron microscopes of the fiber formed using electrospinning process.
Fig. 2 is P（AN-co-AA）Carbon fiber adsorption desorption curve.
Fig. 3 is three-electrode system carbon fiber cyclic voltammogram.
Fig. 4 is three-electrode system carbon fiber constant current charge-discharge curve map.
Embodiment
1st, spinning fibre is prepared：
By 12.1g acrylonitrile, 1.34g acrylic acid, 47.3g dimethyl sulfoxides（DMSO）Three-necked flask is added, adds 0.61g
Azodiisobutyronitrile（AIBN）, it is sufficiently stirred and leads to 20 min of nitrogen, be heated to 60 DEG C, react 12 h, acrylonitrile propylene is made
Acid copolymer P（AN-co-AA）.
Take 0.6g acrylonitrile acrylic copolymers P（AN-co-AA）It is dissolved in 5.4g DMF solvents, is sufficiently stirred 12 h,
Obtain the spinning solution of mass fraction 10%.
Electrostatic spinning operates：Suitable spinning solution is drawn with syringe, and spinning syringe needle is loaded onto on its top, with power supply just
Extremely it is connected.Received with aluminium foil, be connected as anode with receiver board.The fltting speed of flow velocity, that is, syringe of spinning solution is by micro note
Pump control is penetrated, until syringe needle has stable droplet appearance, applies high pressure, it is 16 kV to control voltage, and flow velocity is 0.1 mm/min, is spun
Silk the distance between head and receiver are 14cm, you can obtain continuous acrylonitrile-acrylic acid copolymer nanofiber, such as Fig. 1
It is shown, spinning fibre size uniformity, it is ensured that manufactured fiber does not have bead string phenomenon.
2nd, polyacrylonitrile base co-polymer carbon fiber is prepared：
The preparation process of polyacrylonitrile base co-polymer carbon fiber is carried out in temperature automatically controlled tube furnace, including pre-oxidation and
It is carbonized two stages.
Corundum boat equipped with acrylonitrile-acrylic acid copolymer nanofiber is placed in tube furnace center, keeps quartz ampoule two
End is communicated with air, and heating rate is 1.5 DEG C/min, is warming up to 240 DEG C of insulations and is carried out pre-oxidation treatment 120min, then sealing
Tube furnace, in a nitrogen atmosphere, is warming up to 800 DEG C of progress carbonization treatment 120min with 5 DEG C/min, is cooled to room temperature automatically, i.e.,
Obtain polyacrylonitrile base co-polymer carbon fiber.
3rd, high-specific surface area and high specific capacitance carbon fiber are prepared（That is activating process）：
Polyacrylonitrile base co-polymer carbon fiber after 0.2g is carbonized is mixed with 0.8g KOH, is added 20mL water and is uniformly stirred
Mix.Gained mixture is dried into 12 h in 110 DEG C of baking ovens, dried mixture is placed in tube furnace, is protected in nitrogen stream
Under shield, 5 DEG C/min of programming rate is warming up to 800 DEG C of 60 min of constant temperature of activation temperature, and subsequent tube furnace is down to room temperature.By gained
Product washes away alkaline matter with the HCl/water solution of 1 M, then is washed with deionized water to neutrality, is finally placed in 110 DEG C of baking oven
Dry 24 h, obtain high-specific surface area and high specific capacitance carbon fiber after cooling.
Nitrogen adsorption desorption test is carried out to carbon fiber in 77K as shown in Fig. 2, as seen from Figure 2：In electrostatic spinning process
In, acrylonitrile section is thrown away with acrylic acid section and is mutually mixed, in carbonization, acrylic acid section carboxyl pyrolysis pore-forming.
4th, each performance verification of high-specific surface area and high specific capacitance carbon fiber：
Mass ratio is weighed as 8:1:1 ratio is fine by high-specific surface area made of above method of the present invention and high specific capacitance carbon
Dimension and conductive agent acetylene black, adhesive polytetrafluoroethylene (PTFE)（PTFE）Be put into small mortar, be added dropwise isopropanol, constantly grinding and dropwise
Isopropanol is added dropwise, mixture is uniformly mixed, drop coating is in the nickel foam of 1*5 cm.The good nickel sheet of drop coating is placed in vacuum drying oven
When 80 DEG C of dryings 6 are small, smooth thin slice is pressed into after being cooled to room temperature（10 MPa of pressure）, it is then small with 120 DEG C of dryings 12 again
When.The foam nickel electrode prepared, mercury/mercuric oxide electrode and platinum plate electrode are placed in KOH electrolyte and form the work of three electrodes
System, wherein foam nickel electrode are working electrode, and mercury/mercuric oxide electrode is reference electrode, and platinum plate electrode is to electrode, uses electricity
Chem workstation carries out cyclic voltammetric, obtains figure as shown in Figure 3, and constant current charge-discharge test is as shown in Figure 4.
In Fig. 3, curve A to E represents the cyclic voltammetric obtained under the sweep speed of 5,10,20,50,100 mv/s respectively
Curve, electrode material can keep approximate rectangular topography profile, show that material has well forthright again in the case where sweeping speed greatly
Energy.
Fig. 4, A to E represent the constant current charge-discharge curve obtained under the current density of 10,5,2,1,0.6 A/g respectively,
Different current density lower curves keep approximate isosceles triangle feature, illustrate that material still can under big current density
Enough keep preferable capacitive characteristics.
Claims (7)
1. a kind of method that random copolymer prepares high-specific surface area and high specific capacitance carbon fiber, it is characterised in that including following step
Suddenly：
1）Acrylonitrile acrylic copolymer P is formed by radical polymerization, acrylonitrile acrylic copolymer P is dissolved in N, N- bis-
In methylformamide, the mixing quality ratio of spinning solution, the acrylonitrile acrylic copolymer P and n,N-Dimethylformamide is formed
For 1: 9；Acrylonitrile-acrylic acid copolymer nanofiber is made by electrospinning process；
2）Acrylonitrile-acrylic acid copolymer nanofiber is pre-oxidized successively using tube furnace, carbonization treatment, obtain polypropylene
Itrile group copolymer carbon fiber；The temperature of the carbonization is 800 DEG C, time 120min；
3）Polyacrylonitrile base co-polymer carbon fiber is mixed into post activation with KOH aqueous solutions, obtains high-specific surface area and high specific capacitance carbon
Fiber.
2. according to the method described in claim 1, it is characterized in that：Voltage is 16 kV during the electrostatic spinning, the stream of spinning solution
Speed is 0.1 mm/min, and the distance between spinneret and receiver are 14 cm.
3. according to the method described in claim 1, it is characterized in that：The temperature of the pre-oxidation is 200~300 DEG C, and the time is
120min。
4. according to the method described in claim 3, it is characterized in that：The temperature of the pre-oxidation is 240 DEG C.
5. according to the method described in claim 1, it is characterized in that：The polyacrylonitrile base co-polymer carbon fiber and KOH mix
It is 1: 4 to close mass ratio.
6. according to the method described in claim 1, it is characterized in that：The temperature conditionss of the activation are 700~900 DEG C.
7. according to the method described in claim 6, it is characterized in that：The temperature conditionss of the activation are 800 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN105506784A (en) * | 2016-02-05 | 2016-04-20 | 扬州大学 | Preparation method of composite carbon nanofibers with high specific surface area |
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| CN102936764A (en) * | 2012-11-27 | 2013-02-20 | 天津工业大学 | Preparation method of polyacrylonitrile-based carbon nanofibers |
| CN105506784A (en) * | 2016-02-05 | 2016-04-20 | 扬州大学 | Preparation method of composite carbon nanofibers with high specific surface area |
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| Synthesis and characterization of poly(acrylonitrile-co-acrylic acid) as precursor of carbon nanofibers;Ezgi Ismar等;《polymers advanced technologies》;20160413;第27卷(第10期);第1383-1388页 * |
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