CN104150469A - Method capable of preparing few-layer graphene powder in batches - Google Patents
Method capable of preparing few-layer graphene powder in batches Download PDFInfo
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Abstract
The invention particularly relates to a method capable of preparing few-layer graphene powder in batches. By using various electrolytes as a flocculent floating agent of a graphene colloidal solution, the graphene quickly floats on the upper side of the solution to prepare the graphene powder. According to the method provided by the invention, a diluted graphene oxide solution is reduced by virtue of hydrazine hydrate to form the graphene colloidal solution, so that the reductive graphene is prevented from being agglomerated in a large quantity. By using the flocculent floating agents of electrolyte solutions of acids, bases and alkalis, the graphene is quick to wash, so that the method is simple to operate and beneficial for quantity production and has a wide prospect of large-scaled industrialized application. The diluted solution is used in the method, so that the whole reaction process is less in influence on the environment. Moreover, the waste liquid contains few ions, so that the treatment cost is low.
Description
(1) technical field
The invention belongs to that energy field is micro-, nano material technology of preparing, particularly a kind of method that can the few layer graphene powder of mass preparation.
(2) background technology
Graphene (Graphene) be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the individual layer flat film that honeycomb lattice arrangement forms, and only has the two-dimensional material of a carbon atom thickness, is the elementary cell that builds other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite).Graphene has excellent physical and chemical performance, gradually for fields such as transparent conductive film, nano electron device (transistor, the interconnected internal memory semi-conductor of transistor circuit), conductive ink, solar cell, lithium cell, ultracapacitor, sensor and biological medicines.
One of current method that likely realizes scale operation graphene powder is to adopt Hummers method (Preparation of grapHitic oxide, Journal of the American Chemical Society, 80,1339) method combining with solution reduction: first, graphite is carried out to temperature control intercalation oxide treatment, obtain graphite oxide, the more ultrasonic graphene oxide of peeling off to obtain, then process to obtain Graphene with the reduction of the reductive agent such as hydrazine hydrate, sodium borohydride.Conventionally, strengthen the consumption of reductive agent in order to obtain good reduction effect, the concentration while increasing graphene oxide reduction in order to obtain a large amount of Graphenes fast, thus cause the Graphene reunion of production serious, reduction effect is variation on the contrary.Therefore, in the urgent need to develop a kind of can be in a large number, easily operate, low cost and can prevent that the method that Graphene is reunited from preparing high-quality graphene powder.
(3) summary of the invention
The present invention is in order to make up the deficiencies in the prior art, provide a kind of easily, fast, can mass the method for the few layer of preparation (10 layers following) graphene powder, solve the problems such as Graphene in the preparation process existing in prior art is easily reunited, poorly conductive.
The present invention is achieved through the following technical solutions:
Can prepare a method for layer graphene powder less by mass, its special character is: make the floating reagent of solidifying wadding of Graphene colloidal solution with various ionogen, make Graphene float on fast solution top, prepare graphene powder.
Of the present invention can mass the method for the few layer graphene powder of preparation, comprise the following steps:
(1) graphene oxide: under condition of ice bath, natural graphite mixes with SODIUMNITRATE, adds the vitriol oil, potassium permanganate reaction successively, after reaction, add deionized water, keep 20-30 minute at 90-100 DEG C, then add hydrogen peroxide and deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt alternately centrifuge washing of pickling and washing, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution;
(2) hydrazine hydrate reduction: add deionized water in graphene oxide solution, under agitation add hydrazine hydrate, then add ammoniacal liquor, pH value of solution=9-10, is warming up to 95 DEG C of insulations, obtains Graphene colloidal solution;
(3) the floating suction filtration of solidifying wadding: taking electrolyte solution as solidifying wadding leafing agent, Graphene colloidal solution is mixed with electrolyte solution, room temperature leaves standstill, and washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace; under nitrogen protection; heat up with the temperature rise rate of 2-10 DEG C/min; 1000-1050 DEG C of insulation 2 minutes-3 hours; be cooled to room temperature, afterwards, grind; and with the ultrasonic dispersion of organic solvent, dry to obtain graphene powder for 50-60 DEG C.
Of the present invention can mass the method for the few layer graphene powder of preparation, comprise the following steps:
(1) graphene oxide: under condition of ice bath, 50-100g natural graphite mixes with 25-50g SODIUMNITRATE, add the 1.15-2.3L vitriol oil, add 150-300g potassium permanganate, reaction 1-2 hour, is warming up to 35 DEG C of reaction 30-50 minute again, add afterwards deionized water 0.75-1.5L, keep 20-30 minute at 90-100 DEG C, then add 0.15-0.3L hydrogen peroxide and 7-15L deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt alternately centrifuge washing of pickling and washing, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution;
(2) hydrazine hydrate reduction: add 2L deionized water in the graphene oxide solution of 2L 0.5mg/mL, under agitation add the hydrazine hydrate of 1.4 mL massfractions 50%, then add the ammoniacal liquor of 7mL massfraction 28%, solution PH=9-10, be warming up to 95 DEG C of insulations 1 hour, obtain Graphene colloidal solution;
(3) the floating suction filtration of solidifying wadding: taking electrolyte solution as solidifying wadding leafing agent, Graphene colloidal solution is mixed with electrolyte solution, the wherein volume ratio 1:2 of Graphene colloidal solution and electrolyte solution, room temperature leaves standstill 0.5-2 hour, Graphene is slowly assembled, swim in solution top, washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace; under nitrogen protection; heat up with the temperature rise rate of 2-10 DEG C/min; 1000-1050 DEG C of insulation 2 minutes-3 hours; be cooled to room temperature, afterwards, grind; and with the ultrasonic dispersion of organic solvent, dry to obtain graphene powder for 50-60 DEG C.
Of the present invention can mass the method for the few layer graphene powder of preparation, the ionogen adopting is sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, SODIUMNITRATE, sodium sulfate, sodium-chlor, sodium carbonate, volatile salt, and the massfraction concentration of the electrolyte solution of employing is 5%.
Of the present invention can mass the method for the few layer graphene powder of preparation, organic solvent is alcohols, ketone, aldehydes organic solvent.
Of the present invention can mass the method for the few layer graphene powder of preparation, the number of plies of the graphene powder of the hydrazine hydrate reduction of preparation is 2-5 layer, carbon-to-oxygen ratio is 11.90, specific surface area is 232-346 m
2/ g, specific conductivity is 100-403 S/m.
Of the present invention can mass the method for the few layer graphene powder of preparation, the hydrazine hydrate reduction of preparation is 3-7 layer in the number of plies of the graphene powder of thermal reduction, good crystallinity, carbon-to-oxygen ratio is 86.72, specific surface area is 271-393 m
2/ g, specific conductivity is 1741-2766 S/m.
The invention has the beneficial effects as follows: in the present invention, adopt hydrazine hydrate reduction dilute concentration graphene oxide solution, form Graphene colloidal solution, can prevent a large amount of reunions of reduced graphene self; In the present invention, adopt acid, alkali, salt electrolyte solution for the floating reagent of solidifying wadding, be convenient to the quick washing of Graphene, simple to operate, be beneficial to batch production, there are the bright prospects of heavy industrialization application; The solution that has all adopted dilute concentration in the present invention, whole reaction process is very little on the impact of environment, and only contains a small amount of ion in waste liquid, processing cost is low, the present invention is 2-5 layer by the sheet number of plies that hydrazine hydrate reduction obtains graphene powder, and carbon-to-oxygen ratio is 11.90, and specific surface area is 232-346 m
2/ g, specific conductivity is 100-403 S/m; The sheet number of plies of the graphene powder obtaining after thermal treatment again with hydrazine hydrate reduction is 3-7 layer, good crystallinity, and carbon-to-oxygen ratio is 86.72, specific surface area is 271-393 m
2/ g, specific conductivity is 1741-2766 S/m.
(4) brief description of the drawings
Accompanying drawing 1 is the Raman spectrogram (Raman) of hydrazine hydrate reduction and the hydrazine hydrate reduction Graphene that thermal reduction obtains after processing again;
Accompanying drawing 2 obtains the X X-ray photoelectron spectroscopy X figure (XPS) of the C 1s peak position of Graphene for hydrazine hydrate reduction; Its C/O=11.90;
Accompanying drawing 3 for hydrazine hydrate reduction again thermal reduction process to obtain the X X-ray photoelectron spectroscopy X figure (XPS) of C 1s peak position of Graphene; Its C/O=86.72;
Accompanying drawing 4 obtains the transmission electron microscope picture (TEM) of Graphene for hydrazine hydrate reduction;
Accompanying drawing 5 obtains atomic power (AFM) figure (a) of the Graphene of Graphene for hydrazine hydrate reduction;
Accompanying drawing 6 obtains the height survey sheet (b) of the Graphene of Graphene for hydrazine hydrate reduction; The thickness of Graphene is 1.109 nm;
Accompanying drawing 7 for hydrazine hydrate reduction again thermal reduction process to obtain the transmission electron microscope picture (TEM) of Graphene;
Accompanying drawing 8 for hydrazine hydrate reduction again thermal reduction process to obtain the scanning electron microscope (SEM) photograph (SEM) of Graphene.
(5) embodiment
Embodiment 1
The preparation process of few layer graphene powder:
(1) graphene oxide: adopt Hummers method, under condition of ice bath, 50g natural graphite mixes with 25g SODIUMNITRATE, adds the 1.15L vitriol oil, then adds 150g potassium permanganate, react 2 hours, be warming up to 35 DEG C of reactions 50 minutes, add afterwards deionized water 0.75L, keep 20-30 minute at 90-100 DEG C, then add the deionized water of 0.15L hydrogen peroxide and 7L, obtain glassy yellow graphite oxide solution; Afterwards, sulphuric acid soln and the deionized water of employing 5% are alternately centrifugal, and to sulfate radical-free ion, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution.
(2) hydrazine hydrate reduction: adopt hydrazine hydrate reduction method, in the graphene oxide solution of 2L 0.5mg/mL, add 2L deionized water, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add again 7mL ammoniacal liquor (massfraction 28%), pH value of solution=9-10, be warming up to 95 DEG C of insulations 1 hour, be cooled to 50 DEG C once, obtain Graphene colloidal solution.
(3) the floating suction filtration of solidifying wadding: taking the sulphuric acid soln of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sulphuric acid soln of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 0.5 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is that 2-5 layer, carbon-to-oxygen ratio are 11.90, the about 242.4m of specific surface area
2/ g, specific conductivity approximately 225.7 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1000 DEG C of insulations 30 minutes, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, its number of plies is 3-7 layer, good crystallinity, and carbon-to-oxygen ratio is 86.72, specific surface area approximately 309.4 m
2/ g, specific conductivity approximately 1867.3 S/m.
Embodiment 2
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the hydrochloric acid soln of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the hydrochloric acid soln of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, remove chlorion, wash again the graphene powder that lyophilize obtains hydrazine hydrate reduction, specific surface area approximately 346.1 m
2/ g, specific conductivity approximately 370.7 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 1 hour, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 350.1 m
2/ g, specific conductivity approximately 2174.6 S/m.
Embodiment 3
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the sodium hydroxide solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sodium hydroxide solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 270.1 m
2/ g, specific conductivity approximately 168.1 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 273.4 m
2/ g, specific conductivity approximately 2041.7 S/m.
Embodiment 4
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the potassium hydroxide solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the potassium hydroxide solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 301.3 m
2/ g, specific conductivity approximately 355.8 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1000 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 393.7 m
2/ g, specific conductivity approximately 1741.0 S/m.
Embodiment 5
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the sodium nitrate solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sodium nitrate solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 2 hours, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 271.2 m
2/ g, specific conductivity approximately 353.5 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 318.3 m
2/ g, specific conductivity approximately 1895.0 S/m.
Embodiment 6
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the metabisulfite solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the metabisulfite solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, remove sulfate ion, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 271.1 m
2/ g, specific conductivity approximately 214.0 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 319.3 m
2/ g, specific conductivity approximately 2657.6 S/m.
Embodiment 7
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the sodium chloride solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sodium chloride solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, remove chlorion, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 232.8 m
2/ g, specific conductivity approximately 266.1 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 288.8 m
2/ g, specific conductivity approximately 2766.3 S/m.
Embodiment 8
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the sodium carbonate solution of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sodium carbonate solution of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 257.2 m
2/ g, specific conductivity approximately 403.9 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 2 minutes, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 271.1 m
2/ g, specific conductivity approximately 2118.6 S/m.
[embodiment 9
The preparation process of few layer graphene powder:
(1) graphene oxide: with embodiment one.
(2) hydrazine hydrate reduction: with embodiment one.
(3) the floating suction filtration of solidifying wadding: taking the sal volatile of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sal volatile of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area approximately 260.7 m
2/ g, specific conductivity approximately 100.2 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 10 DEG C/min, 1050 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with alcohol or the ultrasonic dispersion of acetone, dry to obtain graphene powder for 50-60 DEG C, specific surface area approximately 272.8 m
2/ g, specific conductivity approximately 1854.6 S/m.
Embodiment 10
The preparation process of few layer graphene powder:
(1) graphene oxide: adopt Hummers method, under condition of ice bath, 100g natural graphite mixes with 50g SODIUMNITRATE, adds the 2.3L vitriol oil, then adds 300g potassium permanganate, react 1 hour, be warming up to 35 DEG C of reactions 30 minutes, add afterwards deionized water 1.5L, keep 30 minutes at 100 DEG C, then add the deionized water of 0.3L hydrogen peroxide and 15L, obtain glassy yellow graphite oxide solution; Afterwards, sulphuric acid soln and the deionized water of employing 5% are alternately centrifugal, and to sulfate radical-free ion, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution.
(2) hydrazine hydrate reduction: adopt hydrazine hydrate reduction method, in the graphene oxide solution of 2L 0.5mg/mL, add 2L deionized water, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add again 7mL ammoniacal liquor (massfraction 28%), pH value of solution=9-10, be warming up to 95 DEG C of insulations 1 hour, be cooled to 50 DEG C once, obtain Graphene colloidal solution.
(3) the floating suction filtration of solidifying wadding: taking the sulphuric acid soln of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sulphuric acid soln of 2 volumes 5%, room temperature (25 DEG C) leaves standstill 0.5 hour, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is that 3 layers, carbon-to-oxygen ratio are 11.90, the about 240m of specific surface area
2/ g, specific conductivity approximately 230 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 2 DEG C/min, 1025 DEG C of insulations 2 hours, be cooled to room temperature.Afterwards, grind, and with the ultrasonic dispersion of alcohol, dry to obtain graphene powder for 50 DEG C, its number of plies is 5 layers, good crystallinity, and carbon-to-oxygen ratio is 87, specific surface area approximately 312.3 m
2/ g, specific conductivity approximately 1869.6 S/m.
Embodiment 11
The preparation process of few layer graphene powder:
(1) graphene oxide: adopt Hummers method, under condition of ice bath, 75g natural graphite mixes with 37g SODIUMNITRATE, adds the 1.7L vitriol oil, then adds 225g potassium permanganate, react 1.5 hours, be warming up to 35 DEG C of reactions 40 minutes, add afterwards deionized water 1.1L, keep 25 minutes at 95 DEG C, then add the deionized water of 0.22L hydrogen peroxide and 10.5L, obtain glassy yellow graphite oxide solution; Afterwards, sulphuric acid soln and the deionized water of employing 5% are alternately centrifugal, and to sulfate radical-free ion, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution.
(2) hydrazine hydrate reduction: adopt hydrazine hydrate reduction method, in the graphene oxide solution of 2L 0.5mg/mL, add 2L deionized water, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add again 7mL ammoniacal liquor (massfraction 28%), pH value of solution=9-10, be warming up to 95 DEG C of insulations 1 hour, be cooled to 50 DEG C once, obtain Graphene colloidal solution.
(3) the floating suction filtration of solidifying wadding: taking the sulphuric acid soln of massfraction 5% for the solidifying leafing agent of wadding a quilt with cotton, the Graphene colloidal solution of 1 volume is mixed with the sulphuric acid soln of 2 volumes 5%, room temperature (30 DEG C) leaves standstill 2 hours, Graphene is slowly assembled, swim in solution top, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is that 4 layers, carbon-to-oxygen ratio are 11.90, the about 245m of specific surface area
2/ g, specific conductivity approximately 250.4 S/m.
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heat up with the temperature rise rates of 5 DEG C/min, 1025 DEG C of insulations 3 hours, be cooled to room temperature.Afterwards, grind, and with the ultrasonic dispersion of formaldehyde, dry to obtain graphene powder for 55 DEG C, its number of plies is 5 layers, good crystallinity, and carbon-to-oxygen ratio is 87, specific surface area approximately 316.7 m
2/ g, specific conductivity approximately 1864.1 S/m.
The present invention is in the process of the few layer of preparation (below 10 layers) Graphene, and the floating reagent of solidifying wadding using comprises the ionogen such as sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, SODIUMNITRATE, sodium sulfate, sodium-chlor, sodium carbonate, volatile salt.
Embodiment 12
Because the few layer graphene powder characteristic of gained is similar, existing taking the present embodiment 1 as example, be analyzed as follows:
Fig. 1 is the Raman spectrogram of hydrazine hydrate reduction and the hydrazine hydrate reduction Graphene that thermal reduction obtains after processing again, and sample prepared by the D in figure and G peak two kinds of methods of explanation is all that crystallinity is lacked layer graphene preferably;
Fig. 2 is the X X-ray photoelectron spectroscopy X figure (XPS) that hydrazine hydrate reduction obtains the C 1s peak position of Graphene; Wherein C/O=11.90;
Fig. 3 be hydrazine hydrate reduction again thermal reduction process to obtain the X X-ray photoelectron spectroscopy X figure (XPS) of C 1s peak position of Graphene; Wherein C/O=86.72;
Fig. 4 is the transmission electron microscope picture (TEM) that hydrazine hydrate reduction obtains Graphene, shows that this graphene powder comprises a large amount of few layer graphenes;
Fig. 5 is atomic power (AFM) figure (a) that hydrazine hydrate reduction obtains the Graphene of Graphene, contains a large amount of micro-nano thin slices in graphene powder;
Fig. 6 is the height survey sheet (b) of the hydrazine hydrate reduction Graphene that obtains Graphene; The thickness of Graphene is 1.109 nm;
Accompanying drawing 7 for hydrazine hydrate reduction again thermal reduction process to obtain the transmission electron microscope picture (TEM) of Graphene, after sintering, there are a lot of gauffers in this kind of Graphene;
Accompanying drawing 8 for hydrazine hydrate reduction again thermal reduction process to obtain the scanning electron microscope (SEM) photograph (SEM) of Graphene, illustrate that this kind of Graphene is made up of micro-nano of many puffy.
Claims (7)
1. can prepare a method for layer graphene powder less by mass, it is characterized in that: make the floating reagent of solidifying wadding of Graphene colloidal solution with various ionogen, make Graphene float on fast solution top, prepare graphene powder.
According to claim 1 can mass the method for the few layer graphene powder of preparation, it is characterized in that: comprise the following steps:
(1) graphene oxide: under condition of ice bath, natural graphite mixes with SODIUMNITRATE, adds the vitriol oil, potassium permanganate reaction successively, after reaction, add deionized water, keep 20-30 minute at 90-100 DEG C, then add hydrogen peroxide and deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt alternately centrifuge washing of pickling and washing, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution;
(2) hydrazine hydrate reduction: add deionized water in graphene oxide solution, under agitation add hydrazine hydrate, then add ammoniacal liquor, pH value of solution=9-10, is warming up to 95 DEG C of insulations, obtains Graphene colloidal solution;
(3) the floating suction filtration of solidifying wadding: taking electrolyte solution as solidifying wadding leafing agent, Graphene colloidal solution is mixed with electrolyte solution, room temperature leaves standstill, and washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace; under nitrogen protection; heat up with the temperature rise rate of 2-10 DEG C/min; 1000-1050 DEG C of insulation 2 minutes-3 hours; be cooled to room temperature, afterwards, grind; and with the ultrasonic dispersion of organic solvent, dry to obtain graphene powder for 50-60 DEG C.
According to claim 2 can mass the method for the few layer graphene powder of preparation, it is characterized in that: comprise the following steps:
(1) graphene oxide: under condition of ice bath, 50-100g natural graphite mixes with 25-50g SODIUMNITRATE, add the 1.15-2.3L vitriol oil, add 150-300g potassium permanganate, reaction 1-2 hour, is warming up to 35 DEG C of reaction 30-50 minute again, add afterwards deionized water 0.75-1.5L, keep 20-30 minute at 90-100 DEG C, then add 0.15-0.3L hydrogen peroxide and 7-15L deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt alternately centrifuge washing of pickling and washing, pH=5-6, obtains pure graphite oxide solution; Finally, supersound process graphite oxide, makes certain density graphene oxide solution;
(2) hydrazine hydrate reduction: add 2L deionized water in the graphene oxide solution of 2L 0.5mg/mL, under agitation add the hydrazine hydrate of 1.4 mL massfractions 50%, then add the ammoniacal liquor of 7mL massfraction 28%, solution PH=9-10, be warming up to 95 DEG C of insulations 1 hour, obtain Graphene colloidal solution;
(3) the floating suction filtration of solidifying wadding: taking electrolyte solution as solidifying wadding leafing agent, Graphene colloidal solution is mixed with electrolyte solution, the wherein volume ratio 1:2 of Graphene colloidal solution and electrolyte solution, room temperature leaves standstill 0.5-2 hour, Graphene is slowly assembled, swim in solution top, washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction processing: the Graphene of dried hydrazine hydrate reduction is put into tube furnace; under nitrogen protection; heat up with the temperature rise rate of 2-10 DEG C/min; 1000-1050 DEG C of insulation 2 minutes-3 hours; be cooled to room temperature, afterwards, grind; and with the ultrasonic dispersion of organic solvent, dry to obtain graphene powder for 50-60 DEG C.
According to described in claim 2 or 3 can mass the method for the few layer graphene powder of preparation, it is characterized in that: the ionogen of employing is sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, SODIUMNITRATE, sodium sulfate, sodium-chlor, sodium carbonate, volatile salt, the massfraction concentration of the electrolyte solution of employing is 5%.
According to described in claim 2 or 3 can mass the method for the few layer graphene powder of preparation, it is characterized in that: organic solvent is alcohols ketone, aldehydes organic solvent.
According to described in claim 2 or 3 can mass the method for the few layer graphene powder of preparation, it is characterized in that: the number of plies of the graphene powder of the hydrazine hydrate reduction of preparation is 2-5 layer, carbon-to-oxygen ratio is 11.90, specific surface area is 232-346 m
2/ g, specific conductivity is 100-403 S/m.
According to described in claim 2 or 3 can mass the method for the few layer graphene powder of preparation, it is characterized in that: the hydrazine hydrate reduction of preparation is 3-7 layer in the number of plies of the graphene powder of thermal reduction, good crystallinity, carbon-to-oxygen ratio is 86.72, specific surface area is 271-393 m
2/ g, specific conductivity is 1741-2766 S/m.
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