CN108335917B - Preparation method of carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material - Google Patents
Preparation method of carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material Download PDFInfo
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Abstract
A preparation method of a carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material comprises the steps of taking crystalline flake graphite as a raw material, preparing graphene oxide by a Hummer method, carrying out surface modification on the graphene oxide by using ionic liquid to obtain ionic liquid surface modified graphene oxide, adding the ionic liquid surface modified graphene oxide and a polymer into a solvent, and strongly stirring under the action of ultrasonic waves to form an electrostatic spinning solution; and (3) carrying out electrostatic spinning on the electrostatic spinning solution, and carrying out heat treatment on the graphene oxide-polymer electrostatic spinning fiber obtained on the electrostatic spinning receiver to obtain the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber. The advantages are that: the process is reasonable, the performance is stable, the RGO agglomeration can be prevented, the specific surface area is improved, the charge storage density and the charge transfer rate are further increased, the RGO super-capacitor can be used as an electrode of a high-capacity power super-capacitor, and the charge and discharge efficiency can reach 99.5-99.7%.
Description
Technical Field
The invention belongs to the field of electrode material preparation, and relates to a preparation method of a carbon nanofiber loaded embedded ordered vertically-arranged reduced graphene oxide electrode material.
Background
Reduced Graphene Oxide (RGO) is generally formed by compounding several to several tens of layers of single graphene, and has the characteristics of an open two-dimensional structure, a high specific surface area, a rapid in-layer electron transfer rate and the like, so that RGO has an extremely high application value as an electrode material in chemical power sources such as a supercapacitor and the like. However, the application of RGO as an electrode material has the problems of serious agglomeration, easy interlayer combination, difficult molding and processing and the like. The one-dimensional (1D) high-length-diameter-ratio nanowire loaded two-dimensional (2D) RGO can form a three-dimensional (3D) reticular membrane structure, so that RGO agglomeration is prevented, the charge storage surface area is increased, and the charge transmission rate and the electrode forming and processing performance are improved. The electrostatic spinning method is the only method which can continuously prepare the nano fiber with high length-diameter ratio at present, and has obvious industrialized characteristics.
CN 103938366A discloses a method for preparing a graphene oxide and polyvinyl alcohol composite membrane by electrostatic spinning, which comprises the following steps: adding graphene oxide into deionized water, carrying out ultrasonic dispersion, and mixing the uniformly dispersed graphene oxide aqueous solution with polyvinyl alcohol to obtain a spinning solution of graphene oxide and polyvinyl alcohol. And then carrying out electrostatic spinning on the spinning solution of the graphene oxide and the polyvinyl alcohol to obtain the graphene oxide and polyvinyl alcohol composite membrane. However, this method does not reduce graphene oxide to obtain RGO, and cannot be used as an electrode active material. CN 104332640A discloses a preparation method of an RGO/nano carbon fiber composite electrode. Uniformly mixing the graphene oxide and the polymer spinning solution, preparing a composite nanofiber membrane by an electrostatic spinning method, and then carrying out heat treatment to obtain the required RGO-carbon nanofiber composite electrode. However, the prepared RGO is coated by the carbon fiber, so that the prepared RGO has the problems of agglomeration, stacking and the like in the carbon nanofiber, and the RGO cannot exert the characteristics of two-dimensional open structure and high specific surface area.
The addition of other nanoparticles can reduce problems of agglomeration and stacking between RGOs. CN105185994A discloses an RGO-doped porous carbon/ferroferric oxide nano-fiber lithium battery negative electrode material and a preparation method thereof. The porous carbon/ferroferric oxide nano-fiber lithium battery cathode material doped with the RGO is obtained by preparing polyacrylonitrile/polymethyl methacrylate nano-fiber doped with ferric salt and RGO by using an electrostatic spinning technology and carrying out preoxidation and high-temperature carbonization. CN 106159211A also adopts a similar method to prepare the carbon/cobalt/RGO composite nanofiber lithium ion battery cathode material. CN 105098160A discloses an RGO-doped hollow porous carbon/silicon nanofiber lithium battery negative electrode material and a preparation method thereof. The preparation method comprises the steps of taking a mixed solution of polyacrylonitrile/polymethyl methacrylate/ethyl orthosilicate/graphene oxide as a shell solution, taking a polymethyl methacrylate solution as a core solution, obtaining polyacrylonitrile/polymethyl methacrylate/silicon dioxide nano fibers doped with graphene oxide by using a coaxial electrostatic spinning technology, and carbonizing at high temperature to obtain the RGO-doped hollow porous carbon/silicon nano fiber lithium battery cathode material. However, the graphene oxide prepared by the methods has poor compatibility in a spinning solution, and the polymer fiber has a small load on the graphene oxide. The prepared RGO-based composite material is embedded in the electrostatic spinning fiber, and the characteristics of two-dimensional open structure and high specific surface area cannot be well shown.
Preparing the graphene oxide and polyacrylonitrile mixed electrostatic spinning fiber by Zhou (Zhou) of North Dakota State university, and the like, and performing heat treatment at 800 ℃ to obtain the RGO/carbon superfine fiber composite electrode material. The RGO/carbon superfine fiber composite electrode material has the advantages of high capacity, high power density and long cycle life. Using graphene oxide and polyacrylonitrile as spinning precursors at Yu (university of Harbin engineering) and the like to obtain NH after electrospinning fibers3Carbonizing in the environment to obtain the radial graphene fiber. However, graphene in the graphene-based fibers obtained by the two methods has the problems of small bulk density, poor orderliness, insufficient processability and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a high-energy-storage-density power type carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material.
The technical solution of the invention is as follows:
a preparation method of a carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material comprises the following specific preparation steps:
(1) preparation of graphene oxide
Taking 10.0g of crystalline flake graphite with 1000 meshes to 5000 meshes as raw materials, and taking 200.0mL to 400.0mL of concentrated sulfuric acid and 4.0 mL ofSodium nitrate (g-6.0 g) and 0.5g H.5 g2O2And 20.0g to 40.0g of potassium permanganate strong oxidant, preparing graphene oxide by adopting a Hummer method to obtain a graphene oxide aqueous solution with an O/C ratio of 0.3 to 0.5;
treating 200.0mL of graphene oxide aqueous solution for 10-30 min by using an ultrasonic crusher with the frequency of 60.0-100.0 KHz and the power of 1.0-3.0 KW; under the action of ultrasonic cavitation and the action of sulfuric acid, potassium permanganate and an oxidant, the graphene oxide is crushed and stripped to obtain a graphene oxide solution with the thickness of a graphene oxide sheet layer of 10.0-30.0 nm and the size of the sheet of 0.1-2 mu m;
removing acid and ions of the obtained graphene oxide solution in deionized water by adopting a semipermeable membrane, purifying, replacing the deionized water outside the semipermeable membrane every 6h until the pH of the solution outside the semipermeable membrane is 7, and drying the obtained graphene oxide at 40 ℃ in vacuum for 12h for later use;
(2) surface modification of graphene oxide
Dissolving 10.0g of graphene oxide prepared in the step (1) in deionized water, and adding 0.1-0.5 g of ionic liquid containing reactive groups, wherein the ionic liquid containing reactive groups is ionic liquid containing carboxyl (-COOH) and ionic liquid containing sulfonic acid groups (-SO)3OH) containing amino groups (-NH)3) The ionic liquid or the ionic liquid containing hydroxyl (-OH) modifies the surface of the graphene oxide; the active functional group at the tail end of the ionic liquid reacts with an oxygen-containing group (-OH, -C ═ O and-COOH) on the surface of the graphene oxide, and positive ionic liquid cations are bonded to the surface of the graphene oxide; the organic group carried by the ionic liquid can ensure that RGO is uniformly and stably dispersed into the electrostatic spinning solution;
after the graphene oxide is modified by the surface of the ionic liquid, the modified graphene oxide with good solubility in an organic solvent and strong surface charge accumulation capacity is obtained;
carrying out centrifugal separation on the ionic liquid modified graphene oxide for 10-30 minutes under the condition of 10000-12000 r/min, and removing supernatant in a centrifugal tube; taking out the ionic liquid modified graphene oxide obtained at the bottom of the centrifugal tube, and vacuum-drying at 40 ℃ for 12 h;
(3) preparation of carbon nanofiber loaded embedded ordered vertical array RGO composite material
Adding 1.0g of ionic liquid surface modified graphene oxide and a polymer into a solvent according to the mass ratio of 1: 100-10: 100, and strongly stirring for 4.0-8.0 h under the action of 300W ultrasonic waves to form an electrostatic spinning solution with the ionic liquid surface modified graphene oxide and the polymer solid content of 20.0-30.0 wt%;
carrying out electrostatic spinning on the electrostatic spinning solution, carrying out heat treatment on the graphene oxide-polymer electrostatic spinning fiber obtained on an electrostatic spinning receiver, heating the fiber from room temperature to 120 ℃ at the heating rate of 0.3-0.5 ℃/min in the air atmosphere, and keeping the temperature at 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at a heating rate of 0.5 ℃/min to 1.5 ℃/min, and keeping the temperature at 280 ℃ for 2 hours; in the argon atmosphere, under the condition that the heating rate is 3.0 ℃/min-5.0 ℃/min, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours, so that the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber is obtained.
Further, the ionic liquid containing a reactive group is 1, 2-dimethyl-3-hydroxyethylimidazole p-methylbenzenesulfonate, 1, 2-dimethyl-3-hydroxyethylimidazole bis (trifluoromethanesulfonyl) imide salt, 1, 2-dimethyl-3-hydroxyethylimidazole hexafluorophosphate, 1, 2-dimethyl-3-hydroxyethylimidazole tetrafluoroborate, 1-hydroxyethyl-2, 3-dimethylimidazole chloride salt, 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1-carboxyethyl-3-methylimidazolium nitrate, 1-carboxyethyl-3-methylimidazolium bisulfate, 1-carboxyethyl-3-methylimidazolium bromide salt, or a salt thereof, 1-carboxyethyl-3-methylimidazole chloride salt, N-butylpyridine sulfonate p-toluenesulfonate, N-butylpyridine sulfonate triflate, N-butylpyridine bisulfate, butylpyridine sultone sulfonate, N-propylpyridine sulfonate p-toluenesulfonate, N-propylpyridine sulfonate triflate, N-propylpyridine bisulfate, propylpyridine sultone sulfonate, 1-butylsulfonic acid-3-methylimidazole trifluoroacetate, 1-butylsulfonic acid-3-methylimidazole trifluoromethanesulfonate and the like.
Further, the polymer is one of polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride, polybenzimidazole and polyimide.
Further, the solvent is one of N, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, concentrated sulfuric acid, acetic acid, dichloromethane and tetrachloromethane.
Furthermore, the electrostatic spinning distance is 8.0 cm-12.0 cm, the electrostatic spinning voltage is 5.0 kV-10.0 kV, and the electrostatic spinning flow rate is 3.0 mL/h-5.0 mL/h.
Furthermore, when the graphene oxide is subjected to surface modification by using the ionic liquid containing the reactive group, the reaction temperature is 60 ℃, and the reaction time is 6 hours.
Further, when the graphene oxide is prepared by the Hummer method in the step (1), 10.0g of 1000-5000 mesh natural crystalline flake graphite is slowly added into a 2000mL big beaker filled with 200-400.0 mL of concentrated sulfuric acid under stirring, the temperature is maintained at 0 +/-1 ℃, then a mixture of 4.0-6.0 g of sodium nitrate and 20.0-40.0 g of potassium permanganate is slowly added, the reaction is completely maintained under stirring at 0 +/-1 ℃ for 2 hours, the temperature is kept for 30 minutes under stirring in a 35 +/-3 ℃ constant-temperature water bath, 460mL of water is slowly added, the temperature is raised to 98 ℃, and the temperature is maintained for 15 minutes under the temperature; diluting to 1400mL with warm water, pouring into 0.5g H2O2The mixture is filtered while hot, and the filter cake is washed thoroughly with 5% HC1 until the filtrate is supplemented with BaC12Solution detection of no SO4 2-At 50 ℃ in P2O5And drying in vacuum for 24 hours in the presence of the graphene oxide, sealing and storing to prepare the graphene oxide aqueous solution with the O/C ratio of 0.3-0.5.
Preparation of carbon nanofiber loaded RGO electrode capacitor vertically and orderly arranged
Cutting the composite material vertically and orderly arranged on the surface of the carbon nanofiber in an RGO embedded mode into electrode slices with the diameter of 3.0cm and the thickness of 300 mu m, bonding the electrode slices on the surface of a metal collector by using a conductive adhesive, and then carrying out vacuum drying at 80 ℃ for 12 hours; polypropylene diaphragm paper is used as an electrode diaphragm, a proper amount of electrolyte is added, and a laminated super capacitor is assembled in a glove box with the water content of less than 100ppm in the argon atmosphereThe specific capacitance of the super capacitor is 223.1CP/F·g-1-231.6CP/F·g-1The charge-discharge efficiency is 99.5% -99.7%; the ionic liquid electrolyte is one of brominated 1-propyl-3-methylimidazole, 1-butyl-3-methylimidazole trifluoromethanesulfonate and 1-ethyl-3-methylimidazole tetrafluoroborate.
The surface energy-modified graphene oxide with specific size and thickness is used as an additive component and is mixed with a polymer to prepare an electrostatic spinning solution. By controlling the electrostatic spinning process conditions, the orientation and arrangement of the graphene oxide in the electrostatic spinning fibers are controlled, and the composite material with the graphene oxide orderly and vertically arrayed on the surface of the polymer electrostatic spinning fibers is obtained. Then the composite electrode active material with RGO vertically and orderly arranged on the surface of the carbon nano fiber is obtained through the processes of pre-oxidation, carbonization, activation and the like.
The invention has the beneficial effects that:
1. under the action of strong ultrasonic cavitation shock waves, with the help of the strong oxidation effect of sulfuric acid, potassium permanganate, hydrogen peroxide and sodium nitrate strong oxidant in the preparation process of graphene oxide, not only can the graphene oxide lamella be stripped, but also the graphene oxide can be cut along the structural defect part on the surface of the graphene oxide, and the nano-micron graphene oxide with a certain graphene oxide lamella thickness, size and surface oxidation degree can be obtained.
2. The graphene oxide is modified by the surface of the functional ionic liquid, so that the solubility of the graphene oxide in an electrostatic spinning solution can be increased, the agglomeration can be prevented, the compatibility of the graphene oxide and a polymer can be improved, and the ionic liquid cation has high polarizability and charge storage capacity. Therefore, the charge accumulation capacity of the modified graphene oxide in the electrostatic spinning process can be improved, the electric field force of the graphene oxide in a high-voltage electrostatic field and the repulsive force between the graphene oxide are increased, and the controllability of the orientation and arrangement of the graphene oxide in the electrostatic spinning fibers is controlled.
3. In the process of carrying out high-voltage electrostatic spinning on the electrostatic spinning solution, the surface of the graphene oxide is subjected to a larger electric field force in the electrostatic spinning process, so that the graphene oxide is perpendicular to the direction of the electric field force in the electrostatic spinning process and is oriented towards an electrostatic spinning collector. Meanwhile, due to the fact that the graphene oxides are the same in electric property, mutual repulsion force is generated, and stacking and agglomeration of the graphene oxides are prevented. By controlling parameters of the electrostatic spinning process, the electric field force, gravity, repulsion force, adhesion force and other effects on the graphene oxide in the electrostatic spinning process are balanced. And under the adhesion, wrapping and loading effects of the polymer electrospun fibers, the surface modified graphene oxide is deposited on the collector along with the polymer electrospun fibers to obtain the graphene oxide-polymer electrospun fiber surface composite material. After heat treatment, the RGO-carbon nanofiber composite material can be obtained.
4. The composite electrode material with RGOs vertically and orderly arranged on the surface of the carbon nanofiber is formed by connecting two-dimensional RGOs (2D) in series through one-dimensional carbon nanofibers (1D) to form a composite fiber membrane electrode (3D) material with a three-dimensional structure. The RGO agglomeration can be prevented, the specific surface area is improved, the conductivity and the electrode processability are improved, the charge storage density and the charge transfer rate are further increased, the electrode can be used as an electrode of a high-capacity power type super capacitor, and the charge and discharge efficiency can reach 99.5-99.7%.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a constant current charge and discharge curve for different current densities for an RGO-carbon nanofiber material electrode supercapacitor of the present invention (corresponding to example 1); the result shows that the RGO-carbon nanofiber electrode capacitor has higher energy storage density and better mass specific capacitance characteristic;
FIG. 3 is a cyclic voltammetry test curve for an RGO-carbon nanofiber electrode supercapacitor of the invention (corresponding to example 1); the result shows that the RGO-carbon nanofiber electrode capacitor still keeps higher charge-discharge efficiency under the condition of high charge-discharge power and shows high specific power characteristic;
FIG. 4 is an AC impedance spectrum of an RGO-carbon nanofiber electrode supercapacitor of the present invention (corresponding to example 1); the result shows that the good three-dimensional network system of the carbon nanofiber and the good conductivity of the RGO form good synergistic complementary action, and compared with a pure RGO and carbon nanofiber electrode capacitor, the impedance is one order of magnitude smaller;
FIG. 5 is a Scanning Electron Microscope (SEM) image of RGO of the present invention (corresponding to example 1);
FIG. 6 is a Scanning Electron Microscope (SEM) image of carbon nanofibers of the present invention (corresponding to example 1);
FIG. 7 is a Scanning Electron Microscope (SEM) image of RGO loaded with embedded ordered array arrangement of carbon nanofibers according to the present invention (corresponding to example 1).
Detailed Description
EXAMPLE 1 preparation of RGO-carbon nanofiber composites
The process flow is shown in figure 1, and the specific preparation steps are as follows:
(1) preparation of surface modified graphene oxide
Slowly adding 10.0g of 5000-mesh natural crystalline flake graphite into a 2000mL big beaker filled with 200mL of concentrated sulfuric acid under stirring, keeping the temperature at (0 +/-1) ° C, slowly adding a mixture of 4g of sodium nitrate and 20g of potassium permanganate, keeping the temperature at (0 +/-1) ° C under stirring for 2 hours to completely react, keeping the temperature for 30 minutes under stirring in a constant-temperature water bath at (35 +/-3) ° C, slowly adding 460mL of water, raising the temperature to 98 ℃, and keeping the temperature for 15 minutes under the temperature; diluting to 1400mL with warm water, and pouring a certain amount of 0.5g H2O2The filter cake was thoroughly washed with 5 wt% HC1 by filtration while hot until the filtrate was free of SO4 2-(by BaC12Solution assay) at 50 ℃ in P2O5Drying in vacuum for 24 hours in the presence of the graphene oxide, sealing and storing to prepare a graphene oxide aqueous solution with an O/C ratio of 0.3-0.5;
treating a graphene oxide aqueous solution for 30 minutes under the action of ultrasonic waves with the frequency of 60kHz and the power of 1.0kW to obtain a graphene oxide dispersion solution with the thickness of a graphene oxide sheet layer of 10.0-30.0 nm and the size of the sheet of 0.1-2 mu m; removing acid and ions from the obtained graphene oxide dispersion solution in deionized water by adopting a semipermeable membrane, and replacing the deionized water outside the semipermeable membrane every 2h until the pH value of the solution outside the semipermeable membrane is 7; vacuum drying the graphene oxide obtained in the semipermeable membrane for 12 hours at 40 ℃ for later use; (2) surface modification of graphene oxide
Taking 10.0g of dried graphene oxide and 0.1g of 1, 2-dimethyl-3-hydroxyethyl imidazole p-methyl benzene sulfonate, putting into 100mL of deionized water, and reacting at 60 ℃ for 6 hours to bond ionic liquid sulfonic acid groups with hydroxyl, carboxyl and epoxy groups on the surface of the graphene oxide to obtain graphene oxide with the ionic liquid surface modified; placing the solution in a centrifuge, centrifuging for 10 minutes at 12000 r/min, removing supernatant in the centrifuge tube, and repeating the centrifuging process for 3 times; taking out the ionic liquid surface modified graphene oxide obtained at the bottom of the centrifugal tube, and vacuum-drying at 40 ℃ for 12 h;
(3) preparation of carbon nanofiber loaded embedded ordered vertical array RGO composite material
Dissolving 1.0g of ionic liquid surface modified graphene oxide and 60.0g of polyacrylonitrile in 210.0mL of N, N' -dimethylformamide, and strongly stirring for 6.0h under the action of 300W ultrasonic waves to obtain a mixed electrostatic spinning precursor solution; carrying out electrostatic spinning on the mixed solution under the conditions of electrostatic spinning voltage of 10.0kV, spinning distance of 8.0cm and flow rate of 3.0mL/h to obtain graphene oxide-polyacrylonitrile mixed electrostatic spinning fibers;
carrying out heat treatment on the graphene oxide-polyacrylonitrile mixed electro-spun fiber, heating the fiber from room temperature to 120 ℃ at a heating rate of 0.3 ℃/minute in an air atmosphere, and keeping the temperature at 120 ℃ for 2 hours; heating from 120 ℃ to 280 ℃ at the heating rate of 1.5 ℃/min, and keeping the temperature at 280 ℃ for 2 h; in the argon atmosphere, under the condition that the heating rate is 3.0 ℃/minute, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours, so that the RGO embedded ordered composite material vertically arranged on the surface of the carbon nanofiber is obtained.
Preparation of carbon nanofiber electrode capacitor
Cutting the carbon nanofiber load vertically and orderly arranged RGO membrane into electrode slices with the diameter of 3.0cm and the thickness of 300 mu m, bonding the surface of a metal collector by using a conductive adhesive, and then drying the electrode slices in vacuum at 80 ℃ for 12 hours. The laminated supercapacitor is assembled by taking polypropylene diaphragm paper as an electrode diaphragm and brominated 1-propyl-3-methylimidazole ionic liquid as electrolyte in a glove box with the water content less than 100ppm in an argon atmosphere. The test results are shown in table 1, the constant current charge-discharge curve of the supercapacitor is shown in fig. 2, the cyclic voltammetry curve is shown in fig. 3, the alternating current impedance spectrum is shown in fig. 4, and the SEM photograph of the carbon nanofiber-supported RGO is shown in fig. 7. As can be seen from the SEM photographs of FIGS. 5-7, the present invention can effectively arrange the RGO embedded ordered array on the surface of the carbon fiber with nanometer and micron size (FIG. 5), avoid the stacking and agglomeration of RGO, improve the specific surface area and utilization rate of RGO, and increase the charge storage density. Meanwhile, the carbon fibers with the nanometer and micron sizes play a role in bridging among the RGOs, so that the RGOs are connected into a three-dimensional network structure, and the high conductivity of the RGOs can promote the conductivity of the carbon fibers, thereby improving the overall conductivity and the formability and processability of the membrane electrode.
EXAMPLE 2 preparation of RGO-carbon nanofiber composites
(1) Preparation of surface modified graphene oxide
Taking 10.0g of 3000-mesh crystalline flake graphite as a raw material, adding 300.0mL of concentrated sulfuric acid, 5.0g of sodium nitrate, 30.0g of potassium permanganate and 0.5g H2O2Preparing graphene oxide by adopting an improved Hummer method to obtain a graphene oxide aqueous solution with an O/C ratio of 0.3-0.5;
treating a graphene oxide aqueous solution for 10 minutes under the action of ultrasonic waves with the frequency of 80kHz and the power of 2.0kW to obtain the graphene oxide solution with the thickness of a graphene oxide sheet layer of 10.0-30.0 nm and the size of the sheet of 0.1-2 microns;
removing acid and ions from the obtained graphene oxide solution in deionized water by adopting a semipermeable membrane, replacing the deionized water outside the semipermeable membrane every 2h until the pH value of the solution outside the semipermeable membrane is 7, and drying the graphene oxide obtained in the semipermeable membrane in vacuum at 40 ℃ for 12h for later use;
(2) surface modification of graphene oxide
Taking 10.0g of dried graphene oxide and 0.3g of 1-carboxyethyl-3-methylimidazole hydrogen sulfate, and reacting in 100mL of deionized water at 60 ℃ for 6h to bond an ionic liquid sulfuric acid group with hydroxyl, carboxyl and epoxy groups on the surface of the graphene oxide, thereby obtaining the ionic liquid surface modified graphene oxide. Placing the solution after ultrasonic treatment in a centrifuge, centrifuging for 20 minutes at 11000 r/min, removing supernatant in a centrifuge tube, and repeating the centrifuging process for 3 times. Taking out the ionic liquid surface modified graphene oxide obtained at the bottom of the centrifugal tube, and vacuum-drying at 40 ℃ for 12 h;
(3) preparation of carbon nanofiber loaded embedded ordered vertical array RGO composite material
1.0g of ionic liquid surface modified graphene oxide and 10.0g of polymethyl methacrylate are dissolved in 50.0mL of N-methyl pyrrolidone, and the mixture is stirred strongly for 4.0h under the action of 300W ultrasonic waves to obtain a mixed electrostatic spinning precursor solution. Carrying out electrostatic spinning on the mixed solution under the conditions of electrostatic spinning voltage of 8.0kV, spinning distance of 10.0cm and flow rate of 5.0mL/h to obtain the graphene oxide-polymethyl methacrylate mixed electrostatic spinning fiber;
carrying out heat treatment on the graphene oxide-polymethyl methacrylate mixed electro-spinning fiber, heating the fiber from room temperature to 120 ℃ at a heating rate of 0.4 ℃/min in an air atmosphere, and keeping the temperature at 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at the heating rate of 0.5 ℃/min, and keeping the temperature at 280 ℃ for 2 h; in the argon atmosphere, the temperature is raised from 280 ℃ to 1000 ℃ at the temperature raising rate of 4.0 ℃/minute, and the temperature is kept at 1000 ℃ for 2 hours, so that the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber is obtained.
Preparation of carbon nanofiber electrode capacitor
Cutting the carbon nanofiber load vertically and orderly arranged RGO membrane into electrode slices with the diameter of 3.0cm and the thickness of 300 mu m, bonding the surface of a metal collector by using a conductive adhesive, and then drying the electrode slices in vacuum at 80 ℃ for 12 hours. The laminated supercapacitor is assembled by using polypropylene diaphragm paper as an electrode diaphragm and an acetonitrile solution of tetraethylammonium tetrafluoroborate as an electrolyte in a glove box with water content less than 100ppm in an argon atmosphere. The test results are shown in table 1.
EXAMPLE 3 preparation of RGO-carbon nanofiber composites
(1) Preparation of surface modified graphene oxide
Taking 10.0g of 1000-mesh flake graphite as a raw material, adding 400mL of concentrated sulfuric acid, 6.0g of sodium nitrate, 40.0g of potassium permanganate and 0.5g H2O2Preparing graphene oxide by adopting an improved Hummer method to obtain a graphene oxide aqueous solution with an O/C ratio of 0.3-0.5;
treating a graphene oxide aqueous solution for 20min under the action of ultrasonic waves with the frequency of 100kHz and the power of 3.0kW to obtain a graphene oxide dispersion solution with the thickness of a graphene oxide sheet layer of 10.0-30.0 nm and the size of the sheet of 0.1-2 microns;
removing acid and ions from the obtained graphene oxide dispersion solution in deionized water by adopting a semipermeable membrane, replacing the deionized water outside the semipermeable membrane every 2h until the pH value of the solution outside the semipermeable membrane is 7, and drying the graphene oxide obtained in the semipermeable membrane in vacuum at 40 ℃ for 12h for later use;
(2) surface modification of graphene oxide
Taking 10.0g of dried graphene oxide and 0.5g of 1-carboxyethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt to react for 6 hours in 100mL of deionized water at 60 ℃, so that carboxyl of the ionic liquid is bonded with hydroxyl, carboxyl and epoxy groups on the surface of the graphene oxide, and the graphene oxide with the modified ionic liquid surface is obtained; placing the graphene oxide solution with the surface modified by the ionic liquid into a centrifuge, centrifuging for 20 minutes under the condition of 10000 revolutions per minute, removing supernatant in a centrifuge tube, and repeating the centrifuging process for 3 times. Taking out the ionic liquid surface modified graphene oxide obtained at the bottom of the centrifugal tube, and vacuum-drying at 40 ℃ for 12 h;
(3) preparation of carbon nanofiber loaded embedded ordered vertical array RGO composite material
1.0g of ionic liquid surface modified graphene oxide and 100.0g of polybenzimidazole are dissolved in 500.0mL of N, N' -dimethylacetamide, and the mixture is stirred strongly for 8.0h under the action of 300W ultrasonic waves to obtain a mixed electrostatic spinning precursor solution. Carrying out electrostatic spinning on the mixed solution under the conditions of electrostatic spinning voltage of 9.0kV, spinning distance of 9.0cm and flow rate of 5.0mL/h to obtain the graphene oxide-polybenzimidazole mixed electrostatic spinning fiber;
carrying out heat treatment on the graphene oxide-polybenzimidazole mixed electrospun fiber, heating the fiber from room temperature to 120 ℃ at a heating rate of 0.5 ℃/min in an air atmosphere, and keeping the temperature at 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at the heating rate of 1.0 ℃/min, and keeping the temperature at 280 ℃ for 2 h; in the argon atmosphere, under the condition that the heating rate is 5.0 ℃/min, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours, so that the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber is obtained.
Preparation of carbon nanofiber electrode capacitor
Cutting the carbon nanofiber loaded RGO membrane which is vertically and orderly arranged into electrode slices with the diameter of 3.0cm and the thickness of 300 mu m, bonding the surface of a metal collector with a conductive adhesive, and then carrying out vacuum drying at 80 ℃ for 12 h; the laminated supercapacitor is assembled by taking polypropylene diaphragm paper as an electrode diaphragm and taking propylene carbonate solution of triethyl-methyl ammonium tetrafluoroborate as electrolyte in a glove box with water content less than 100ppm in argon atmosphere. The test results are shown in table 1.
Comparative example 1 preparation of RGO:
(1) preparation of graphene oxide
Taking 10.0g of crystalline flake graphite with 200 meshes as a raw material, and adding 200.0mL of concentrated sulfuric acid, 4.0g of sodium nitrate, 20.0g of potassium permanganate and 0.5g H2O2Preparing graphene oxide by adopting an improved Hummer method; 500mL of the mixed solution of the graphene oxide and the strong oxidant prepared by the Hummer method is treated for 30 minutes under the action of ultrasonic waves with the frequency of 60KHz and the power of 1.0 KW; and (3) removing acid and ions from the obtained graphene oxide solution by adopting a semipermeable membrane in deionized water, and replacing the deionized water outside the semipermeable membrane every 2h until the pH value of the solution outside the semipermeable membrane is 7. Vacuum drying the graphene oxide obtained in the semipermeable membrane for 12 hours at 40 ℃ for later use;
(2) preparation of RGO: heating the graphene oxide from room temperature to 120 ℃ at a heating rate of 0.3 ℃/min in an air atmosphere, and keeping the temperature of 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at the heating rate of 0.5 ℃/min, and keeping the temperature at 280 ℃ for 2 h; in the argon atmosphere, under the condition that the heating rate is 3.0 ℃/min, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours to obtain RGO;
(3) preparation of RGO electrode capacitors
Adding 5.0g of the RGO into 4.0g of polytetrafluoroethylene emulsion with the mass percentage concentration of 25 wt%, and adding deionized water to prepare slurry with the solid content of 30 wt%; ultrasonically dispersing for 10 minutes at the frequency of 15kHz and 200W, and then mechanically stirring for 2 hours to obtain electrode slurry; coating the prepared electrode slurry on the surface of an aluminum foil current collector to obtain an electrode slice with the thickness of 0.3 mu m, and shearing the electrode slice into an electrode slice with the diameter of 3.0cm after vacuum drying at 120 ℃ for 24 hours. Polypropylene diaphragm paper is used as an electrode diaphragm, 1.0mol/L of tetraethylene ammonium tetrafluoroborate/acetonitrile is used as electrolyte, a button type super capacitor is assembled, and the electrochemical performance is tested and is shown in table 1.
Comparative example 2 preparation of carbon nanofiber
(1) Preparation of polyacrylonitrile electrostatic spinning fiber
10.0g of polyacrylonitrile was dissolved in 50mL of N, N' -dimethylformamide to obtain an electrospinning precursor solution. Carrying out electrostatic spinning under the conditions of electrostatic spinning voltage of 8.0kV, spinning distance of 7.0cm and flow rate of 3.0mL/h to obtain polyacrylonitrile electrostatic spinning fibers;
(2) preparation of polyacrylonitrile-based superfine carbon fiber
Heating from room temperature to 120 ℃ at the heating rate of 0.2 ℃/min, and keeping the temperature at 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at the heating rate of 0.5 ℃/min, and keeping the temperature at 280 ℃ for 2 h; in the argon atmosphere, under the condition that the heating rate is 2.0 ℃/minute, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours, so that the polyacrylonitrile-based carbon nanofiber membrane is obtained.
Cutting the carbon nanofiber membrane into electrode plates with the diameter of 3.0cm and the thickness of 300 mu m, bonding the surface of the metal collector with a conductive adhesive, and then carrying out vacuum drying at 120 ℃ for 12 h; polypropylene diaphragm paper is used as an electrode diaphragm, brominated 1-propyl-3-methylimidazole ionic liquid is used as electrolyte, and a laminated supercapacitor is assembled in a glove box with the water content less than 100ppm in the argon atmosphere for electrochemical test. The electrochemical properties are shown in table 1.
| Electrode for electrochemical cell | Specific capacitance (C)P/F·g-1) | Internal resistance (R)int/Ω) | Charge-discharge efficiency (η/%) |
| Comparative example 1 | 193.3 | 5.5 | 97.1 |
| Comparative example 2 | 186.7 | 6.2 | 96.8 |
| Example 1 | 231.6 | 0.5 | 99.7 |
| Example 2 | 223.1 | 0.8 | 99.5 |
| Example 3 | 227.3 | 0.7 | 99.6 |
From the electrochemical data analysis in table 1, it can be known that, compared with the RGO electrode and the ultrafine carbon fiber electrode, the carbon nanofiber-loaded RGO electrode super capacitor can significantly improve the energy storage density of the super capacitor by about 40% or more, reduce the internal resistance by about 1 order of magnitude, and improve the charge-discharge efficiency by 2 percentage points. The reason is that the specific surface area and the specific surface area utilization rate of the RGO are obviously improved due to the loading of the carbon fibers, and the conductivity of the carbon fibers and the conductivity of the whole membrane electrode can be improved due to the embedding of the ordered array of the RGO. Therefore, the nanofiber-loaded RGO electrode maintains good power characteristics and charge-discharge efficiency while improving the specific capacitance of the supercapacitor.
In the high-voltage electrostatic spinning process, the surface modified graphene oxide is charged with the same charges by the high-voltage electrostatic field, and the graphene oxide is orderly arranged in the electrostatic spinning solution at intervals due to the repulsion effect between the charges, so that the stacking and agglomeration of the graphene oxide are avoided. Under the action of the high-voltage electrostatic field, the graphene oxide with different charges is arranged in the direction perpendicular to the direction of the electric field force and facing the direction of the electrostatic spinning receiving plate. The graphene oxide is sprayed out along with polymer electrostatic spinning jet flow, and when the viscosity of electrostatic spinning fibers borne by the graphene oxide is larger than or equal to the gravity, the graphene oxide is loaded in the electrostatic spinning fibers and is solidified into the graphene oxide-polymer fiber composite material. After heat treatment, the composite material with the graphene oxide embedded ordered vertical array arranged in the polymer electrostatic spinning fiber is obtained.
The above description is only exemplary of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of a carbon nanofiber loaded orderly-arranged reduced graphene oxide electrode material is characterized by comprising the following steps of:
the preparation method comprises the following specific steps:
(1) preparation of graphene oxide
Taking 10.0g of 1000-5000 mesh crystalline flake graphite as a raw material, and preparing graphene oxide by using 200.0-400.0 mL of concentrated sulfuric acid, 4.0-6.0 g of sodium nitrate, 0.5g of hydrogen peroxide and 20.0-40.0 g of potassium permanganate strong oxidant by adopting a Hummer method to obtain a graphene oxide aqueous solution with an O/C ratio of 0.3-0.5;
treating a graphene oxide aqueous solution for 10-30 min by using an ultrasonic crusher with the frequency of 60.0-100.0 KHz and the power of 1.0-3.0 KW to obtain a graphene oxide dispersion solution with the thickness of a graphene oxide sheet layer of 10.0-30.0 nm and the size of 0.1-2 mu m;
removing acid and ions of the obtained graphene oxide dispersion solution in deionized water by adopting a semipermeable membrane, purifying the obtained graphene oxide dispersion solution by adopting deionized water, replacing the deionized water outside the semipermeable membrane every 6h until the pH of the solution outside the semipermeable membrane is =7, and drying the obtained graphene oxide at 40 ℃ for 12h in vacuum for later use;
(2) surface modification of graphene oxide
Dissolving 10.0g of graphene oxide prepared in the step (1) in deionized water, and adding 0.1-0.5 g of ionic liquid containing reactive groups, wherein the ionic liquid containing reactive groups is ionic liquid containing carboxyl (-COOH) groups and ionic liquid containing sulfonic groups (-SO)3OH) containing amino groups (-NH)3) The ionic liquid or the ionic liquid containing hydroxyl (-OH) modifies the surface of the graphene oxide; when the surface is modified, the reaction temperature is 60 ℃, and the reaction time is 6 hours;
carrying out centrifugal separation on the ionic liquid modified graphene oxide for 10-30 minutes under the condition of 10000-12000 rpm, and removing supernatant in a centrifugal tube; taking out the ionic liquid modified graphene oxide obtained at the bottom of the centrifugal tube, and vacuum-drying at 40 ℃ for 12 h;
(3) preparation of carbon nanofiber loaded embedded ordered vertical array RGO composite material
Adding 1.0g of ionic liquid surface modified graphene oxide and a polymer into a solvent according to a mass ratio of 1: 100-10: 100, and stirring for 4.0-8.0 h under the action of 300W ultrasonic waves to form an electrostatic spinning solution with the ionic liquid surface modified graphene oxide and the polymer solid content of 20.0-30.0 wt%;
carrying out electrostatic spinning on the electrostatic spinning solution, wherein the electrostatic spinning interval is 8.0-12.0 cm, the electrostatic spinning voltage is 5.0-10.0 kV, the electrostatic spinning flow rate is 3.0-5.0 mL/h, carrying out heat treatment on the graphene oxide-polymer electrostatic spinning fiber obtained on an electrostatic spinning receiver, heating the graphene oxide-polymer electrostatic spinning fiber to 120 ℃ from room temperature under the condition that the heating rate is 0.3-0.5 ℃/min in air atmosphere, and keeping the temperature at 120 ℃ for 2 h; heating from 120 ℃ to 280 ℃ at a heating rate of 0.5 ℃/min to 1.5 ℃/min, and keeping the temperature at 280 ℃ for 2 hours; in the argon atmosphere, under the condition that the heating rate is 3.0 ℃/min to 5.0 ℃/min, the temperature is raised from 280 ℃ to 1000 ℃, and the temperature is kept constant at 1000 ℃ for 2 hours, so that the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber is obtained.
2. The preparation method of the carbon nanofiber supported ordered arrangement reduced graphene oxide electrode material as claimed in claim 1, wherein the preparation method comprises the following steps:
the ionic liquid containing the reactive group is 1, 2-dimethyl-3-hydroxyethylimidazole p-methylbenzenesulfonate, 1, 2-dimethyl-3-hydroxyethylimidazole bis (trifluoromethanesulfonyl) imide salt, 1, 2-dimethyl-3-hydroxyethylimidazole hexafluorophosphate, 1, 2-dimethyl-3-hydroxyethylimidazole tetrafluoroborate, 1-hydroxyethyl-2, 3-dimethylimidazole chloride salt, 1-carboxyethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide salt, 1-carboxyethyl-3-methylimidazole nitrate, 1-carboxyethyl-3-methylimidazole hydrogensulfate, 1-carboxyethyl-3-methylimidazole bromide salt, 1-carboxyethyl-3-methylimidazole chloride salt, or,N-sulfonic acid butyl pyridine p-toluene sulfonate,N-sulfonic acid butyl pyridine triflate,N-butylpyridinium hydrogen sulfate sulfonate, butylpyridinolide sulfonate,N-sulfonic acid propyl pyridine p-toluene sulfonate,N-sulfonic acid propyl pyridine triflate,N-one of propyl pyridine bisulfate sulfonate, propyl pyridine lactone sulfonate, 1-butyl sulfonic acid-3-methylimidazole trifluoroacetate and 1-butyl sulfonic acid-3-methylimidazole trifluoromethanesulfonate.
3. The preparation method of the carbon nanofiber supported ordered arrangement reduced graphene oxide electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: the polymer is one of polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride, polybenzimidazole and polyimide.
4. The preparation method of the carbon nanofiber supported ordered arrangement reduced graphene oxide electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: the solvent isN,N-dimethylformamide,N-one of methyl pyrrolidone, dimethyl sulfoxide, tetrahydrofuran, concentrated sulfuric acid, acetic acid, dichloromethane, and tetrachloromethane.
5. The method of claim 1The application of the RGO embedded composite material vertically and orderly arranged on the surface of the carbon nanofiber, which is prepared by the preparation method of the carbon nanofiber-loaded orderly-arranged reduced graphene oxide electrode material, in a super capacitor is characterized in that: cutting the composite material vertically and orderly arranged on the surface of the carbon nanofiber in an RGO embedded mode into electrode slices with the diameter of 3.0cm and the thickness of 300 mu m, bonding the electrode slices on the surface of a metal collector by using a conductive adhesive, and then carrying out vacuum drying at 80 ℃ for 12 hours; polypropylene diaphragm paper is used as an electrode diaphragm, a proper amount of electrolyte is added, and a laminated super capacitor is assembled in a glove box with the water content of less than 100ppm in the argon atmosphere, wherein the specific capacitance of the super capacitor is 223.1C P/F·g-1-231.6C P/F·g-1The charge-discharge efficiency is 99.5% -99.7%; the ionic liquid electrolyte is one of brominated 1-propyl-3-methylimidazole, 1-butyl-3-methylimidazole trifluoromethanesulfonate and 1-ethyl-3-methylimidazole tetrafluoroborate.
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