CN108335917A - A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material - Google Patents
A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material Download PDFInfo
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- CN108335917A CN108335917A CN201810076444.1A CN201810076444A CN108335917A CN 108335917 A CN108335917 A CN 108335917A CN 201810076444 A CN201810076444 A CN 201810076444A CN 108335917 A CN108335917 A CN 108335917A
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- 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
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- 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
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material, using crystalline flake graphite as raw material, graphene oxide is prepared using Hummer methods, graphene oxide is subjected to surface modification with ionic liquid, ionic liquid surface modified graphene oxide is obtained, is added in solvent with polymer, under ul-trasonic irradiation, strong stirring forms electrostatic spinning solution；Electrostatic spinning solution is subjected to electrostatic spinning, by electrostatic spinning graphene oxide polymer electrospun fibers received on the receiver, after Overheating Treatment, obtains the inserted vertical ordered arrangements of RGO in the composite material on carbon nanofibers surface.Advantage is：Rational technology, performance are stablized, and can prevent RGO from reuniting, increasing specific surface area, and then increase charge storage density and charge migration rate, the electrode as high-capacity power type ultracapacitor and use, and efficiency for charge-discharge can reach 99.5% 99.7%.
Description
Technical field
The invention belongs to electrode material preparation field, it is related to a kind of embedded orderly vertical arrangement of carbon nanofibers load also
The preparation method of former graphene oxide electrode material.
Background technology
Redox graphene (RGO) is typically to be combined to tens layers monolithic graphite alkene by several layers of, has and opens
Two-dimensional structure, the characteristics such as electron transfer rate in high-specific surface area and quick layer, make RGO as electrode material in super electricity
Great application value in the electrochmical power sources such as container.But RGO applies serious, the easy interlayer in the presence of reunion compound as electrode material
The problems such as difficult with processing and forming.Three-dimensional can be formed using nanowire supported two dimension (2D) RGO of one-dimensional (1D) high length-diameter ratio
(3D) netted membrane structure, to prevent RGO from reuniting, increase charge storage surface area, improve charge transport rate and electrode moulding
Processing performance.Method of electrostatic spinning is the unique method that can continuously prepare high length-diameter ratio nanofiber at present, and industrialization feature is aobvious
It writes.
CN 103938366A disclose a kind of method that electrostatic spinning prepares graphene oxide and composite membrane of polyvinyl alcohol,
It includes the following steps：It adds graphene oxide into deionized water, after ultrasonic disperse, by finely dispersed graphene oxide water
Solution and polyvinyl alcohol obtain the spinning solution of graphene oxide and polyvinyl alcohol.Then by graphene oxide and poly- second
The spinning solution of enol carries out electrostatic spinning, obtains graphene oxide and composite membrane of polyvinyl alcohol.But this method is not carried out
The reduction of graphene oxide obtains RGO, can not be used as electrode active material.CN 104332640A disclose a kind of RGO/
Carbon nano-fiber method for preparing composite electrode.Graphene oxide is uniformly mixed with polymer dope, passes through electrostatic spinning
Method prepares composite nano-fiber membrane, subsequently heat-treated to obtain required RGO- carbon nano-fibers combination electrode.But it prepares
RGO by Carbon fibe coat wherein, make its in carbon nanofibers exist reunite, stack the problems such as, RGO two dimension open architectures
It can not be played with high-specific surface area characteristic.
By adding the problems such as other nano-particle methods can reduce reunion and stacking between RGO.CN
105185994A disclose it is a kind of doping RGO porous carbon/ferriferrous oxide nano fiber lithium cell cathode material and its preparation
Method.It is to prepare doping molysite and polyacrylonitrile/polymethyl methacrylate nano fibre of RGO using electrostatic spinning technique
Dimension obtains porous carbon/ferriferrous oxide nano fiber lithium cell cathode material of doping RGO by pre-oxidizing with high temperature cabonization.
CN106159211 A are also prepared for carbon/cobalt/RGO composite nano fiber lithium ion battery negative materials using similar method.
CN105098160 A disclose it is a kind of doping RGO hollow porous carbon/silicon nanofiber lithium cell cathode material and its preparation
Method.It is molten as shell using the mixed solution of polyacrylonitrile/polymethyl methacrylate/ethyl orthosilicate/graphene oxide
Liquid obtains doping graphene oxide using polymethyl methacrylate solution as sandwich layer solution using coaxial electrostatic spinning technology
Polyacrylonitrile/polymethyl methacrylate/silicon dioxide nano fiber, after high temperature cabonization, obtain the hollow porous of doping RGO
Carbon/silicon nanofiber lithium cell cathode material.But the graphene oxide of above-mentioned several method poor compatibility in spinning solution,
And polymer fiber is few to graphene oxide-loaded amount.The RGO based composites of preparation are embedded in electrospun fibers,
The characteristic of its two-dimentional open architecture and high-specific surface area could not be showed well.
North Dakota State University's week (Zhou) etc. prepares graphene oxide and polyacrylonitrile mixing electrospun fibers, passes through
RGO/ charcoal superfine fibre combination electrode materials are obtained after crossing 800 DEG C of heat treatments.RGO/ charcoal superfine fibre combination electrode materials have
Large capacity, high power density and long circulation life.Harbin Engineering University is with graphene oxide and polyacrylonitrile in (Yu) etc.
Spinning presoma obtains NH after electrospinning fibre3Charing obtains radial graphene fiber in environment.But above two method obtains
To graphene-based fiber in graphene there are bulk densities it is small, order is poor and processing performance is insufficient the problems such as.
Invention content
The technical problem to be solved in the present invention is to provide a kind of high energy storage density power-type carbon nanofibers to load orderly row
The preparation method of row redox graphene electrode material.
Technical solution of the invention is：
A kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material, specific preparation process
It is as follows：
(1), the preparation of graphene oxide
It is raw material to take the mesh crystalline flake graphite of 1000 mesh of 10.0g~5000, with the concentrated sulfuric acid of 200.0mL~400.0mL, 4.0g~
6.0g sodium nitrate, 0.5g H2O2With 20.0g~40.0g potassium permanganate strong oxidizers, graphene oxide is prepared using Hummer methods,
O/C is obtained than the graphene oxide water solution for 0.3~0.5；
200.0mL graphene oxide water solutions are taken, using frequency 60.0KHz~100.0KHz, power 1.0KW~3.0KW's is super
Sonication instrument handles 10min~30min；Under ultrasonic cavitation effect, the work of sulfuric acid, potassium permanganate strong oxidizer in addition
With the broken and stripping to graphene oxide progress obtains graphene oxide layer thickness in 10.0nm~30.0nm, piece size
0.1 μm~2 μm of graphene oxide solution；
The graphene oxide solution of gained is deacidified in deionized water, deionization purifying using semi-permeable membrane, is replaced per 6h
Deionized water outside semi-permeable membrane, until outer pH value of solution=7 of semi-permeable membrane, after 40 DEG C of vacuum drying 12h of graphene oxide of gained,
It is spare；
(2), the surface of graphene oxide is modified
Graphene oxide prepared by the step of taking 10.0g (1) is dissolved in deionized water, and containing for addition 0.1g~0.5g can react
Property group ionic liquid, it is described containing reactable group ionic liquid be the ionic liquid containing carboxyl (- COOH), contain sulphur
Acidic group (- SO3OH ionic liquid) contains amino (- NH3) ionic liquid or containing hydroxyl (- OH) ionic liquid, to oxygen
Graphite alkene has carried out surface modification；The active function groups of ionic liquid end and surface of graphene oxide oxygen-containing group (-
OH ,-C=O and-COOH) it reacts, positively charged ionic liquid cation is bonded in surface of graphene oxide；Ionic liquid
Body with organic group can make RGO uniformly, stablize be distributed in electrostatic spinning solution；
Graphene oxide is modified by ionic liquid surface, obtains favorable solubility in organic solvent and surface charge accumulation energy
The strong modified graphene oxide of power；
By ion liquid modified graphene oxide, under the conditions of 10000 revs/min~12000 revs/min, 10 points are centrifuged
Clock~30 minute remove centrifuge tube clear liquid at the middle and upper levels；The ion liquid modified graphene oxide that bottom of the tube obtains will be centrifuged to take
Go out, 12h is dried in vacuo at 40 DEG C；
(3), carbon nanofibers load the preparation of embedded orderly orthogonal array RGO composite materials
1.0g ionic liquids surface modified graphene oxide is taken, with polymer according to mass ratio 1:100~10:100 be added to it is molten
In agent, under 300W ul-trasonic irradiations, strong stirring 4.0h~8.0h, formed ionic liquid surface modified graphene oxide and
Polymer solids level is the electrostatic spinning solution of 20.0wt%~30.0wt%；
Electrostatic spinning solution is subjected to electrostatic spinning, by electrostatic spinning graphene oxide-polymeric electrostatic received on the receiver
Spinning fibre is heat-treated, in air atmosphere, under the conditions of 0.3 DEG C~0.5 DEG C/min of heating rate, by room temperature to
120 DEG C, in 120 DEG C of constant temperature 2h；Under the conditions of 0.5 DEG C/min~1.5 DEG C/min of heating rate, 280 are warming up to by 120 DEG C
DEG C, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 3.0 DEG C/min~5.0 DEG C/min, by 280 DEG C
1000 DEG C are warming up to, after 1000 DEG C of constant temperature 2h, obtains the inserted vertical ordered arrangements of RGO in the compound of carbon nanofibers surface
Material.
Further, it is described containing reactable group ionic liquid be 1,2- dimethyl -3- hydroxyethyl imidazoles to methyl
Bis- (fluoroform sulphonyl) inferior amine salts of benzene sulfonate, 1,2- dimethyl -3- hydroxyethyl imidazoles, 1,2- dimethyl -3- ethoxy miaows
Azoles hexafluorophosphate, 1,2- dimethyl -3- hydroxyethyl imidazoles tetrafluoroborate, 1- ethoxy -2,3- methylimidazoles villaumite, 1-
Bis- (fluoroform sulphonyl) inferior amine salts of carboxyethyl -3- methylimidazoles, 1- carboxyethyl -3- methylimidazolium nitrates, 1- carboxyethyls -3-
Methylimidazolium hydrogen sulphate salt, 1- carboxyethyl -3- methylimidazoles bromide, 1- carboxyethyl -3- methylimidazole villaumites, N- sulfonic acid butyl
Pyridinium p-toluenesulfonate, N- sulfonic acid butyl-pyridiniums fluoroform sulphonate, N- sulfonic acid butyl-pyridiniums disulfate, sulfonic acid butyl pyrrole
Pyridine lactone, N- propyl sulfonic acids pyridinium p-toluenesulfonate, N- propyl sulfonic acid pyridines fluoroform sulphonate, N- propyl sulfonic acid pyridine sulphur
Sour hydrogen salt, propyl sulfonic acid pyridine lactone, 1- butyl sulfonic acid -3- methylimidazoles trifluoroacetate, 1- butyl sulfonic acid -3- methylimidazoles
It is a kind of in trifluoro-methanyl sulfonate etc..
Further, the polymer is polyacrylonitrile, polymethyl methacrylate, Kynoar, polyphenyl and miaow
It is a kind of in azoles, polyimides.
Further, the solvent is n,N-Dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), tetrahydrochysene
One kind in furans, the concentrated sulfuric acid, acetic acid, dichloromethane, tetrachloromethane.
Further, electrostatic spinning spacing 8.0cm~12.0cm, electrostatic spinning voltage 5.0kV~10.0kV, electrostatic spinning
Flow velocity 3.0mL/h~5.0mL/h.
Further, when to graphene oxide with having carried out surface modification containing reactable group ionic liquid, reaction
Temperature is 60 DEG C, reaction time 6h.
Further, when step (1) prepares graphene oxide using Hummer methods, by the mesh day of 1000 mesh of 10.0g~5000
Right crystalline flake graphite is added slowly with stirring in the large beaker of the 2000mL equipped with 200mL~400.0mL concentrated sulfuric acids, temperature dimension
It holds at 0 ± 1 DEG C, is slow added into the mixture of 4.0g~6.0g sodium nitrate and 20.0g~40.0g potassium permanganate, under stiring
0 ± 1 DEG C is maintained, 2h is with the reaction was complete, in 35 ± 3 DEG C of waters bath with thermostatic control, heat preservation 30min under stirring, slow plus people's 460mL water,
Make temperature rise to 98 DEG C, maintains 15min at this temperature；It is diluted to 1400mL with warm water, pours into 0.5g H2O2, mistake while hot
Filter, filter cake is fully washed with 5%HC1, until using BaC1 in filtrate2Solution is detected without SO4 2-, in 50 DEG C in P2O5In the presence of in
Vacuum drying for 24 hours, is sealed, prepares O/C than the graphene oxide water solution for 0.3~0.5.
The preparation of carbon nanofibers loaded vertical ordered arrangement RGO electrode capacitors
Composite material by the inserted vertical ordered arrangements of RGO in carbon nanofibers surface is cut out as diameter 3.0cm, thickness
300 μm of electrode slice is cohered with conductive adhesive behind metal collector surface, 80 DEG C of vacuum drying 12h；With polypropylene every
Film paper is electrode diaphragm, fills appropriate electrolyte, in argon gas atmosphere, water content ＜ 100ppm glove boxes, is assembled into stacked
The specific capacitance of ultracapacitor, the ultracapacitor is 223.1CP/F·g-1-231.6CP/F·g-1, efficiency for charge-discharge is
99.5%-99.7%；The il electrolyte is bromination 1- propyl -3- methylimidazoles, 1- butyl -3- methylimidazole trifluoros
It is a kind of in mesylate and 1- ethyl -3- methyl imidazolium tetrafluoroborates.
Use specific dimensions, the surface of thickness changes energy graphene oxide for adding ingredient, with mixed with polymers preparation electrostatic
Spinning solution.By control electrostatic spinning process condition, orientation and arrangement of the graphene oxide in electrospun fibers are controlled,
Obtain the composite material that the orderly orthogonal array of graphene oxide is arranged in polymer electrospun fibers surface.Then pass through pre- oxygen
The processes such as change, charing and activation, obtain the vertical ordered arrangements of RGO in the composite electrode active material on carbon nanofibers surface.
The beneficial effects of the invention are as follows：
1, under the conditions of intense ultrasonic wave cavitation shock wave, by sulfuric acid in graphene oxide preparation process, potassium permanganate, double
The strong oxidation of oxygen water and sodium nitrate strong oxidizer, not only may be implemented the stripping to graphene oxide layer, but also can be with
Along the fault of construction position of surface of graphene oxide, the cutting to graphene oxide is realized, can obtain with certain oxidation
Graphene film layer thickness, size and surface oxidation degree receive micron-scale graphene oxide.
2, graphene oxide is modified by functional ionic liquids surface, can not only increase graphene oxide in electrostatic spinning
Dissolubility in solution prevents from reuniting, and improves its compatibility with polymer, and ionic liquid cation have it is higher can
Polarizability and charge storage.It is thus possible to improve charge accumulated energy of modified graphene oxide during electrostatic spinning
Power increases the repulsive force between graphene oxide electric field force and graphene oxide suffered in high-voltage electrostatic field, control oxidation
The controllability that graphene is orientated and is arranged in electrospun fibers.
3, electrostatic spinning solution carry out high-voltage electrostatic spinning during, graphene oxide during electrostatic spinning surface by
To larger electric field force effect so that graphene oxide during electrostatic spinning perpendicular to electric field force direction, towards Static Spinning
Silk collector is orientated.Meanwhile mutually exclusive power is generated, graphite oxide is prevented since institute's charging property is identical between graphene oxide
The stacking of alkene and reunion.By controlling electrostatic spinning procedure parameter so that graphene oxide was subject to during electrostatic spinning
The effects that electric field force, gravity, repulsion and adhesion strength, reaches balance.Surface modified graphene oxide is in polymer electrospun fibers
Stick, wrap up and load effect under, as polymer electrospun fibers deposit on collector, obtain graphene oxide-
The composite material on polymer electrospun fibers surface.RGO- carbon nanofibers composite materials can be obtained after heat treatment.
4, the vertical ordered arrangements of RGO are in the combination electrode material on carbon nanofibers surface, by one-dimensional carbon nanofibers
Two-dimensional RGO (2D) is connected, forms composite fibre membrane electrode (3D) material with three-dimensional structure by (1D).It can prevent RGO
Reunion, increasing specific surface area increase electric conductivity and electrode processability, and then increase charge storage density and charge migration speed
Rate, the electrode as high-capacity power type ultracapacitor use, and efficiency for charge-discharge can reach 99.5%-99.7%.
Description of the drawings
Fig. 1 is the process flow chart of the present invention；
Fig. 2 is under the RGO- carbon nanofibers material electrodes ultracapacitor difference current densities of (corresponding embodiment 1) of the invention
Constant current charge-discharge curve；As a result show that RGO- carbon nanofibers electrode capacitors have higher energy storage density, compared with
Good quality compares capacitance characteristic；
Fig. 3 is the cyclic voltammetry curve of the RGO- carbon nanofibers electrode super capacitors of (corresponding embodiment 1) of the invention；
As a result RGO- carbon nanofibers electrode capacitor is shown under high charge-discharge power condition, still maintains higher charge and discharge effect
Rate shows high-specific-power characteristic；
Fig. 4 is the AC impedance spectroscopy of the RGO- carbon nanofibers electrode super capacitors of (corresponding embodiment 1) of the invention；As a result
The good three-dimensional network system of display carbon nanofibers and the good electric conductivity of RGO form good synergy complementation, compare
The impedance of small an order of magnitude is shown in simple RGO and carbon nanofibers electrode capacitor；
Fig. 5 is RGO scanning electron microscope (SEM) figure of (corresponding embodiment 1) of the invention；
Fig. 6 is carbon nanofibers scanning electron microscope (SEM) figure of (corresponding embodiment 1) of the invention；
Fig. 7 is the RGO scanning electron microscope that the carbon nanofibers of (corresponding embodiment 1) of the invention load embedded oldered array arrangement
(SEM) figure.
Specific implementation mode
The preparation of 1 RGO- carbon nanofibers composite materials of embodiment
Technological process is as shown in Figure 1, specific preparation process is as follows：
(1), the preparation of surface modified graphene oxide
5000 mesh natural flake graphites of 10.0g are added slowly with stirring to the big burning of the 2000mL equipped with the 200mL concentrated sulfuric acids
In cup, temperature maintains (0 ± 1) DEG C, is slow added into the mixture of 4g sodium nitrate and 20g potassium permanganate, maintains under stiring
(0 ± 1) DEG C, 2h is with the reaction was complete, in (35 ± 3) DEG C water bath with thermostatic control, stirs lower heat preservation 30min, slowly adds people's 460mL water,
Make temperature rise to 98 DEG C, maintains 15min at this temperature；It is diluted to 1400mL with warm water, pours into a certain amount of 0.5g H2O2,
It filters while hot, filter cake is fully washed with 5wt%HC1, until without SO in filtrate4 2-(use BaC12Solution detects), in 50 DEG C in P2O5
In the presence of in vacuum drying for 24 hours, be sealed, prepare O/C than the graphene oxide water solution for 0.3~0.5；
Graphene oxide water solution is taken, handles 30 minutes and is aoxidized at frequency 60kHz, the ul-trasonic irradiation of power 1.0kW
Graphene film layer thickness disperses solution in the graphene oxide of 10.0nm~30.0nm, 0.1 μm~2 μm of piece size；By gained
Graphene oxide dispersion solution deacidified in deionized water using semi-permeable membrane, deionization, per 2h replacement semi-permeable membrane outside
Deionized water, until behind outer pH value of solution=7 of semi-permeable membrane；After 40 DEG C of vacuum drying 12h of graphene oxide of gained in semi-permeable membrane,
It is spare；(2), the surface of graphene oxide is modified
Graphene oxide, 0.1g 1,2- dimethyl -3- hydroxyethyl imidazole toluenesulfonates after taking 10.0g to dry are put into
In 100mL deionized waters, 6h is reacted at 60 DEG C, makes hydroxyl, the carboxyl of ionic liquid sulfonic acid group and surface of graphene oxide
It is bonded with epoxy group, obtains the graphene oxide of ionic liquid surface modification；Solution is placed in a centrifuge, 12000
It under the conditions of rev/min, centrifuges after ten minutes, removes centrifuge tube clear liquid at the middle and upper levels, repeat above-mentioned centrifugal process 3 times；It will be from
The ionic liquid surface modified graphene oxide that heart bottom of the tube obtains takes out, and 12h is dried in vacuo at 40 DEG C；
(3), carbon nanofibers load the preparation of embedded orderly orthogonal array RGO composite materials
1.0g ionic liquids surface modified graphene oxide, 60.0g polyacrylonitrile are dissolved in the N of 210.0mL, N '-dimethyl
In formamide, under 300W ul-trasonic irradiations, strong stirring 6.0h obtains mixing electrostatic spinning precursor liquid；In electrostatic spinning electricity
Under the conditions of pressing 10.0kV, spinning spacing 8.0cm and flow velocity 3.0mL/h, mixed solution electrostatic spinning is carried out, graphite oxide is obtained
The electrospun fibers of alkene-polyacrylonitrile mixing；
Graphene oxide-polyacrylonitrile mixing electricity spinning fibre is heat-treated, in air atmosphere, 0.3 DEG C of heating rate/
Under the conditions of minute, by room temperature to 120 DEG C, in 120 DEG C of constant temperature 2h；Under the conditions of 1.5 DEG C/min of heating rate, by 120 DEG C
280 DEG C are warming up to, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 3.0 DEG C/min, heated up by 280 DEG C
To 1000 DEG C, after 1000 DEG C of constant temperature 2h, the embedded composite woods for being orderly vertically arranged in carbon nanofibers surface of RGO are obtained
Material.
The preparation of carbon nanofibers electrode capacitor
Carbon nanofibers loaded vertical ordered arrangement RGO films are cut out as diameter 3.0cm, the electrode slice that 300 μm of thickness, with leading
After electric binder binder metal current collection pole surface, 80 DEG C of vacuum drying 12h.Using polypropylene diaphragm paper as electrode diaphragm, bromination 1-
Propyl -3- methylimidazole ionic liquids are that electrolyte is assembled into lamination in argon gas atmosphere, water content ＜ 100ppm glove boxes
Formula ultracapacitor.Test result is as shown in table 1, and the constant current charge-discharge curve of the ultracapacitor is as shown in Fig. 2, cycle volt
Pacify curve as shown in figure 3, AC impedance spectroscopy is as shown in figure 4, carbon nanofibers load the SEM photograph of RGO as shown in Fig. 7.From
The SEM photograph of Fig. 5-Fig. 7, which can be seen that the present invention and can effectively be arranged in the embedded oldered arrays of RGO, receives micron-scale
Carbon fiber surface (Fig. 5) avoids stacking and the reunion of RGO, improves RGO specific surface areas and its utilization rate, increases charge and deposit
Store up density.Meanwhile receiving micron-scale Carbon fibe and playing bridging effect between RGO so that RGO is connected as tridimensional network, RGO
High conductivity can promote the electric conductivity of Carbon fibe again, to the electric conductivity for improving membrane electrode entirety and plastic processability
Energy.
The preparation of 2 RGO- carbon nanofibers composite materials of embodiment
(1), the preparation of surface modified graphene oxide
It is raw material to take the 3000 mesh crystalline flake graphites of 10.0g, adds the concentrated sulfuric acid, 5.0g sodium nitrate, 30.0g permanganic acid of 300.0mL
Potassium and 0.5g H2O2, graphene oxide is prepared using improved Hummer methods, obtains O/C than the graphene oxide for 0.3~0.5
Aqueous solution；
Graphene oxide water solution is taken, handles 10 minutes, is aoxidized at frequency 80kHz, the ul-trasonic irradiation of power 2.0kW
Graphene film layer thickness is in 10.0nm~30.0nm, the graphene oxide solution of 0.1 μm~2 μm of piece size；
Gained graphene oxide solution is deacidified in deionized water, deionization using semi-permeable membrane, primary half is replaced per 2h
The outer deionized water of permeable membrane, until behind outer pH value of solution=7 of semi-permeable membrane, by 40 DEG C of vacuum drying of graphene oxide of gained in semi-permeable membrane
It is spare after 12h；
(2), the surface of graphene oxide is modified
1- carboxyethyl -3- methylimidazolium hydrogen sulphate the salt of graphene oxide, 0.3g after taking 10.0g to dry, the 100mL at 60 DEG C
6h is reacted in deionized water, and the hydroxyl, carboxyl and epoxy group of ionic liquid sulfate group and surface of graphene oxide is made to occur
Bonding, obtains the graphene oxide of ionic liquid surface modification.Solution after ultrasonication is placed in a centrifuge, 11000
It under the conditions of rev/min, centrifuges 20 minutes, removes centrifuge tube clear liquid at the middle and upper levels, repeat above-mentioned centrifugal process 3 times.It will centrifugation
The ionic liquid surface modified graphene oxide that bottom of the tube obtains takes out, and 12h is dried in vacuo at 40 DEG C；
(3), carbon nanofibers load the preparation of embedded orderly orthogonal array RGO composite materials
1.0g ionic liquids surface modified graphene oxide, 10.0g polymethyl methacrylates are dissolved in the N- first of 50.0mL
Base pyrrolidones, under 300W ul-trasonic irradiations, strong stirring 4.0h obtains mixing electrostatic spinning precursor liquid.In electrostatic spinning
Under the conditions of voltage 8.0kV, spinning spacing 10.0cm and flow velocity 5.0mL/h, mixed solution electrostatic spinning is carried out, obtains oxidation stone
The electrospun fibers of black alkene-polymethyl methacrylate mixing；
Graphene oxide-polymethyl methacrylate mixing electricity spinning fibre is heat-treated, in air atmosphere, in heating speed
Under the conditions of 0.4 DEG C/min of rate, by room temperature to 120 DEG C, in 120 DEG C of constant temperature 2h；In 0.5 DEG C/min of condition of heating rate
Under, 280 DEG C are warming up to by 120 DEG C, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 4.0 DEG C/min,
1000 DEG C are warming up to by 280 DEG C, after 1000 DEG C of constant temperature 2h, obtains the embedded vertical ordered arrangements of RGO in carbon nanofibers table
The composite material in face.
The preparation of carbon nanofibers electrode capacitor
Carbon nanofibers loaded vertical ordered arrangement RGO films are cut out as diameter 3.0cm, the electrode slice that 300 μm of thickness, with leading
After electric binder binder metal current collection pole surface, 80 DEG C of vacuum drying 12h.Using polypropylene diaphragm paper as electrode diaphragm, tetrafluoro boron
The acetonitrile solution of sour tetraethyl ammonium is electrolyte, in argon gas atmosphere, water content ＜ 100ppm glove boxes, is assembled into stacked super
Grade capacitor.Test result is as shown in table 1.
The preparation of 3 RGO- carbon nanofibers composite materials of embodiment
(1), the preparation of surface modified graphene oxide
It is raw material to take the 1000 mesh crystalline flake graphites of 10.0g, adds the concentrated sulfuric acid, 6.0g sodium nitrate, 40.0g potassium permanganate of 400mL
With 0.5g H2O2, graphene oxide is prepared using improved Hummer methods, obtains O/C than the graphene oxide for 0.3~0.5
Aqueous solution；
Graphene oxide water solution is taken, 20min is handled at frequency 100kHz, the ul-trasonic irradiation of power 3.0kW, is aoxidized
Graphene film layer thickness disperses solution in the graphene oxide of 10.0nm~30.0nm, 0.1 μm~2 μm of piece size；
The graphene oxide dispersion solution of gained is deacidified in deionized water, deionization using semi-permeable membrane, is replaced per 2h
The outer deionized water of semi-permeable membrane, until behind outer pH value of solution=7 of semi-permeable membrane, 40 DEG C of the graphene oxide of gained in semi-permeable membrane is true
It is spare after the dry 12h of sky；
(2), the surface of graphene oxide is modified
Bis- (fluoroform sulphonyl) inferior amine salts of 1- carboxyethyl -3- methylimidazoles of graphene oxide, 0.5g after taking 10.0g to dry
6h is reacted in 100mL deionized waters at 60 DEG C, makes the hydroxyl, carboxyl and epoxy of ionic liquid carboxyl and surface of graphene oxide
Group is bonded, and obtains the graphene oxide of ionic liquid surface modification；By the graphene oxide of ionic liquid surface modification
Solution is placed in a centrifuge, and under the conditions of 10000 revs/min, is centrifuged 20 minutes, is removed centrifuge tube clear liquid at the middle and upper levels, is repeated
Above-mentioned centrifugal process 3 times.The ionic liquid surface modified graphene oxide that bottom of the tube obtains will be centrifuged to take out, vacuum is dry at 40 DEG C
Dry 12h；
(3), carbon nanofibers load the preparation of embedded orderly orthogonal array RGO composite materials
1.0g ionic liquids surface modified graphene oxide, 100.0g polybenzimidazoles are dissolved in the N of 500.0mL, N '-diformazans
Yl acetamide, under 300W ul-trasonic irradiations, strong stirring 8.0h obtains mixing electrostatic spinning precursor liquid.In electrostatic spinning electricity
Under the conditions of pressing 9.0kV, spinning spacing 9.0cm and flow velocity 5.0mL/h, mixed solution electrostatic spinning is carried out, graphite oxide is obtained
The electrospun fibers of alkene-polybenzimidazoles mixing；
Graphene oxide-polybenzimidazoles mixing electricity spinning fibre is heat-treated, in air atmosphere, in heating rate 0.5
Under the conditions of DEG C/min, by room temperature to 120 DEG C, in 120 DEG C of constant temperature 2h；Under the conditions of 1.0 DEG C/min of heating rate, by
120 DEG C are warming up to 280 DEG C, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 5.0 DEG C/min/minute,
1000 DEG C are warming up to by 280 DEG C, after 1000 DEG C of constant temperature 2h, obtains the embedded vertical ordered arrangements of RGO in carbon nanofibers table
The composite material in face.
The preparation of carbon nanofibers electrode capacitor
Carbon nanofibers loaded vertical ordered arrangement RGO films are cut out as diameter 3.0cm, the electrode slice that 300 μm of thickness, with leading
After electric binder binder metal current collection pole surface, 80 DEG C of vacuum drying 12h；Using polypropylene diaphragm paper as electrode diaphragm, tetrafluoro boron
The carbonic allyl ester solution of triethylenetetraminehexaacetic acid base monomethyl ammonium is electrolyte, in argon gas atmosphere, water content ＜ 100ppm glove boxes, group
Dress up stacked ultracapacitor.Test result is as shown in table 1.
The preparation of 1 RGO of comparative example：
(1), the preparation of graphene oxide
It is raw material to take the 200 mesh crystalline flake graphites of 10.0g, adds the concentrated sulfuric acid, 4.0g sodium nitrate, 20.0g potassium permanganate of 200.0mL
With 0.5g H2O2, graphene oxide is prepared using improved Hummer methods；The oxidation stone for taking the above-mentioned Hummer methods of 500mL to prepare
The mixed solution of black alkene and strong oxidizer is handled 30 minutes at frequency 60KHz, the ul-trasonic irradiation of power 1.0KW；By gained
Graphene oxide solution deacidified in deionized water using semi-permeable membrane, deionization, replaced per 2h gone outside a semi-permeable membrane from
Sub- water, until behind outer pH value of solution=7 of semi-permeable membrane.It will be spare after 40 DEG C of vacuum drying 12h of graphene oxide of gained in semi-permeable membrane；
(2), the preparation of RGO：By above-mentioned graphene oxide in air atmosphere, under the conditions of 0.3 DEG C/min of heating rate, by
Room temperature is to 120 DEG C, in 120 DEG C of constant temperature 2h；Under the conditions of 0.5 DEG C/min of heating rate, 280 DEG C are warming up to by 120 DEG C,
In 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 3.0 DEG C/min/minute, 1000 are warming up to by 280 DEG C
DEG C, after 1000 DEG C of constant temperature 2h, obtain RGO；
(3), the preparation of RGO electrode capacitors
4.0g mass percentage concentration 25wt% ptfe emulsions are added in the above-mentioned RGO of 5.0g, deionized water is added and is configured to
Solid content is 30wt% slurries；Disperseed 10 minutes with the frequency ultrasonic wave of 15kHz, 200W, then mechanical agitation 2h, obtains electrode
Slurry；Electrode slurry obtained is obtained into the electrode slice of 0.3 μ m-thick coated on aluminum foil current collector surface, is dried in vacuo at 120 DEG C
After for 24 hours, the electrode slice of a diameter of 3.0cm is cut into.Using polypropylene diaphragm paper as electrode diaphragm, the tetrafluoro boric acid four of 1.0mol/L
Ethylamine/acetonitrile is electrolyte, is assembled into button-shaped ultracapacitor, tests chemical property, chemical property such as 1 institute of table
Show.
The preparation of 2 carbon nanofibers of comparative example
(1), the preparation of polyacrylonitrile electrospun fibers
It takes 10.0g polyacrylonitrile to be dissolved in the N of 50mL, electrostatic spinning precursor liquid is obtained in N '-dimethyl formamide.In Static Spinning
Electrostatic spinning is carried out under the conditions of filament voltage 8.0kV, spinning spacing 7.0cm and flow velocity 3.0mL/h, obtains polyacrylonitrile electrostatic spinning
Fiber；
(2), the preparation of the ultra-fine Carbon fibe of polyacrylonitrile-radical
Under the conditions of 0.2 DEG C/min of heating rate, by room temperature to 120 DEG C, in 120 DEG C of constant temperature 2h；In heating rate 0.5
Under the conditions of DEG C/min, 280 DEG C are warming up to by 120 DEG C, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, heating rate be 2.0 DEG C/
Under the conditions of minute, 1000 DEG C are warming up to by 280 DEG C, after 1000 DEG C of constant temperature 2h, obtains polyacrylonitrile base carbon nano fibrous membrane.
Carbon nanofibers film is cut out as diameter 3.0cm, the electrode slice that 300 μm of thickness coheres gold with conductive adhesive
After belonging to current collection pole surface, 120 DEG C of vacuum drying 12h；Using polypropylene diaphragm paper as electrode diaphragm, bromination 1- propyl -3- methyl miaows
Oxazolinium ion liquid is that electrolyte is assembled into stacked ultracapacitor in argon gas atmosphere, water content ＜ 100ppm glove boxes,
Carry out electro-chemical test.Chemical property is as shown in table 1.
| Electrode | Specific capacitance (CP/F·g-1) | Internal resistance (Rint/Ω) | Efficiency for charge-discharge (η/%) |
| Comparative example 1 | 193.3 | 5.5 | 97.1 |
| Comparative example 2 | 186.7 | 6.2 | 96.8 |
| Embodiment 1 | 231.6 | 0.5 | 99.7 |
| Embodiment 2 | 223.1 | 0.8 | 99.5 |
| Embodiment 3 | 227.3 | 0.7 | 99.6 |
By 1 electrochemical data of table analysis it is found that carbon nanofibers load RGO electrode super capacitors, with RGO electrodes and surpass
Fine carbon fiber electrode is compared, and can be significantly improved the energy storage density about 40% or more of ultracapacitor, be reduced about 1 quantity of internal resistance
Grade and 2 percentage points of efficiency for charge-discharge of raising.This is because the load of Carbon fibe significantly improves the specific surface area and specific surface of RGO
Product utilization rate, and the oldered array of RGO is embedded with the electric conductivity of the electric conductivity that can improve Carbon fibe and entire membrane electrode.Cause
This, nano-fibre supported RGO electrodes while improving ultracapacitor specific capacitance, and maintain its good power characteristic and
Efficiency for charge-discharge.
During high-voltage electrostatic spinning, high-voltage electrostatic field makes like charges on the modified graphene oxide band of surface, that
Around here since the effect of repulsion between like charges makes graphene oxide regular intervals in electrostatic spinning solution arrange, oxygen is avoided
Stacking between graphite alkene and reunion.And the effect of high-voltage electrostatic field makes the graphene oxide with xenogenesis charge perpendicular to electricity
Field force direction is arranged towards electrostatic spinning receiver board direction.Graphene oxide is sprayed with polymer electrospun jet stream, works as oxygen
When the electrospun fibers viscous force >=gravity of graphite alkene being subject to, graphene oxide is supported in electrospun fibers,
It is solidified into graphene oxide-polymer fiber composites.After Overheating Treatment, it is inserted orderly vertical to obtain graphene oxide
Straight composite material of the array arrangement in polymer electrospun fibers.
It these are only specific embodiments of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of carbon nanofibers load ordered arrangement redox graphene electrode material, it is characterized in that：
Specific preparation process is as follows：
(1), the preparation of graphene oxide
It is raw material to take the mesh crystalline flake graphite of 1000 mesh of 10.0g~5000, with the concentrated sulfuric acid of 200.0mL~400.0mL, 4.0g~
6.0g sodium nitrate, 0.5g hydrogen peroxide and 20.0g~40.0g potassium permanganate strong oxidizers, graphite oxide is prepared using Hummer methods
Alkene obtains graphene oxide water solution；
Graphene oxide water solution is taken, frequency 60.0KHz~100.0KHz, the ultrasonic disruption of power 1.0KW~3.0KW are utilized
Instrument handles 10min~30min, obtains graphene oxide layer thickness in 10.0nm~30.0nm, 0.1 μm~2 μm of piece size
Graphene oxide disperses solution；
The graphene oxide dispersion solution of gained is deacidified in deionized water using semi-permeable membrane, deionization purifying, per 6h
The deionized water outside semi-permeable membrane is replaced, until outer pH value of solution=7 of semi-permeable membrane, by 40 DEG C of vacuum drying of graphene oxide of gained
It is spare after 12h；
(2), the surface of graphene oxide is modified
Graphene oxide prepared by the step of taking 10.0g (1) is dissolved in deionized water, and containing for addition 0.1g~0.5g can react
Property group ionic liquid, it is described containing reactable group ionic liquid be the ionic liquid containing carboxyl (- COOH), contain sulphur
Acidic group (- SO3OH ionic liquid) contains amino (- NH3) ionic liquid or containing hydroxyl (- OH) ionic liquid, to oxygen
Graphite alkene has carried out surface modification；
By ion liquid modified graphene oxide, under conditions of 10000 revs/min~12000 revs/min, 10 are centrifuged
Minute~30 minutes, remove centrifuge tube clear liquid at the middle and upper levels；The ion liquid modified graphene oxide that bottom of the tube obtains will be centrifuged to take
Go out, 12h is dried in vacuo at 40 DEG C；
(3), carbon nanofibers load the preparation of embedded orderly orthogonal array RGO composite materials
1.0g ionic liquids surface modified graphene oxide is taken, with polymer according to mass ratio 1:100~10:100 be added to it is molten
In agent, under 300W ul-trasonic irradiations, 4.0h-8.0h is stirred, forms ionic liquid surface modified graphene oxide and polymer
Solid content is in the electrostatic spinning solution of 20.0wt%~30.0wt%；
Electrostatic spinning solution is subjected to electrostatic spinning, by electrostatic spinning graphene oxide-polymeric electrostatic received on the receiver
Spinning fibre is heat-treated, in air atmosphere, under the conditions of 0.3 DEG C/min~0.5 DEG C/min of heating rate, by room temperature liter
Temperature is to 120 DEG C, in 120 DEG C of constant temperature 2h；Under the conditions of 0.5 DEG C/min to 1.5 DEG C/min of heating rate, it is warming up to by 120 DEG C
280 DEG C, in 280 DEG C of constant temperature 2h；In argon gas atmosphere, under the conditions of heating rate is 3.0 DEG C/min to 5.0 DEG C/min, by 280
DEG C 1000 DEG C are warming up to, after 1000 DEG C of constant temperature 2h, obtain inserted vertical ordered arrangement the answering in carbon nanofibers surface of RGO
Condensation material.
2. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：
It is described containing reactable group ionic liquid be 1,2- dimethyl -3- hydroxyethyl imidazoles toluenesulfonate, 1,2-
Bis- (fluoroform sulphonyl) inferior amine salts of dimethyl -3- hydroxyethyl imidazoles, 1,2- dimethyl -3- hydroxyethyl imidazoles hexafluorophosphate,
1,2- dimethyl -3- hydroxyethyl imidazoles tetrafluoroborate, 1- ethoxy -2,3- methylimidazoles villaumite, 1- carboxyethyl -3- methyl
Bis- (fluoroform sulphonyl) inferior amine salts of imidazoles, 1- carboxyethyl -3- methylimidazolium nitrates, 1- carboxyethyl -3- methylimidazole sulfuric acid
Hydrogen salt, 1- carboxyethyl -3- methylimidazoles bromide, 1- carboxyethyl -3- methylimidazole villaumites, N- sulfonic acid butyl-pyridinium p-methyl benzenesulfonic acid
Salt, N- sulfonic acid butyl-pyridiniums fluoroform sulphonate, N- sulfonic acid butyl-pyridiniums disulfate, sulfonic acid butyl-pyridinium lactone, N- sulfonic acid
PropyIpyridine tosilate, N- propyl sulfonic acid pyridines fluoroform sulphonate, N- propyl sulfonic acid pyridines disulfate, sulfonic acid third
Yl pyridines lactone, 1- butyl sulfonic acid -3- methylimidazoles trifluoroacetate, 1- butyl sulfonic acid -3- methylimidazole trifluoromethayl sulfonic acids
It is a kind of in salt etc..
3. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：The polymer is polyacrylonitrile, polymethyl methacrylate, Kynoar, polybenzimidazoles, polyamides
It is a kind of in imines.
4. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：The solvent is N,N-dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), tetrahydrofuran, dense
One kind in sulfuric acid, acetic acid, dichloromethane, tetrachloromethane.
5. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：Electrostatic spinning spacing 8.0cm~12.0cm, electrostatic spinning voltage 5.0kV~10.0kV, electrostatic spinning flow velocity
3.0mL/h~5.0mL/h.
6. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：When to graphene oxide with surface modification has been carried out containing reactable group ionic liquid, reaction temperature is
60 DEG C, reaction time 6h.
7. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
Method, it is characterized in that：When step (1) prepares graphene oxide using Hummer methods, by the natural squama of mesh of 1000 mesh of 10.0g~5000
Piece graphite is added slowly with stirring in the large beaker of the 2000mL equipped with 200mL~400.0mL concentrated sulfuric acids, and temperature maintains
0 ± 1 DEG C, it is slow added into the mixture of 4.0g~6.0g sodium nitrate and 20.0g~40.0g potassium permanganate, maintains 0 under stiring
± 1 DEG C, 2h is with the reaction was complete, in 35 ± 3 DEG C of waters bath with thermostatic control, stirs lower heat preservation 30min, slowly adds people's 460mL water, make temperature
98 DEG C are risen to, maintains 15min at this temperature；It is diluted to 1400mL with warm water, pours into 0.5g H2O2, filter while hot, with 5%
HC1 fully washs filter cake, until using BaC1 in filtrate2Solution is detected without SO4 2-, in 50 DEG C in P2O5In the presence of in vacuum drying
For 24 hours, it is sealed, prepares O/C than the graphene oxide water solution for 0.3~0.5.
8. the preparation side of carbon nanofibers load ordered arrangement redox graphene electrode material according to claim 1
The inserted vertical ordered arrangements of RGO prepared by method in the application of the composite material in ultracapacitor on carbon nanofibers surface,
It is characterized in that：Composite material by the inserted vertical ordered arrangements of RGO in carbon nanofibers surface cut out as diameter 3.0cm,
The electrode slice that 300 μm of thickness is cohered with conductive adhesive behind metal collector surface, 80 DEG C of vacuum drying 12h；With polypropylene
Diaphragm paper is electrode diaphragm, fills appropriate electrolyte, in argon gas atmosphere, water content ＜ 100ppm glove boxes, is assembled into lamination
The specific capacitance of formula ultracapacitor, the ultracapacitor is 223.1CP/F·g-1-231.6CP/F·g-1, efficiency for charge-discharge is
99.5%-99.7%；The il electrolyte is bromination 1- propyl -3- methylimidazoles, 1- butyl -3- methylimidazole trifluoros
It is a kind of in mesylate and 1- ethyl-3-methylimidazole tetrafluoroborates.
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