CN104150469B - Method capable of preparing few-layer graphene powder in batches - Google Patents
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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 preparation technology, particularly a kind of can the method for 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 is formed, and only has the two-dimensional material of a carbon atom thickness, is the elementary cell building 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 the field such as transparent conductive film, nano electron device (transistor, the interconnected memory semiconductor of transistor circuit), conductive ink, solar cell, lithium cell, ultracapacitor, sensor and biological medicine.
Current one of the method for scale operation graphene powder that likely realizes adopts Hummers method (Preparation of grapHitic oxide, Journal of the American Chemical Society, 80,1339) method combined with solution reduction: first, graphite is carried out temperature control intercalation oxide treatment, graphite oxide, more ultrasonicly peel off to obtain graphene oxide, then obtain Graphene with the reduction treatment of the reductive agent such as hydrazine hydrate, sodium borohydride.Usually, strengthen the consumption of reductive agent to obtain good reduction effect, in order to obtain concentration when a large amount of Graphenes increases graphene oxide reduction fast, thus cause the Graphene produced to reunite serious, reduction effect is deteriorated on the contrary.Therefore, a kind ofly can to operate in a large number, easily in the urgent need to developing, low cost and the method that can prevent Graphene from reuniting to be to prepare 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 one easily, fast, can the method for few layer (the less than 10 layers) graphene powder of mass preparation, in the preparation process existed in solution prior art Graphene easily reunite, the problem such as poorly conductive.
The present invention is achieved through the following technical solutions:
Can prepare the method lacking layer graphene powder by mass, its special character is: the floating reagent of solidifying wadding making Graphene colloidal solution with various ionogen, makes Graphene float on superjacent fast, prepare graphene powder.
Of the present invention can the method for the few layer graphene powder of mass 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, deionized water is added after reaction, keep 20-30 minute at 90-100 DEG C, then add hydrogen peroxide and deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt pickling and the washing of washing alternating centrifugal, 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: with electrolyte solution for solidifying wadding leafing agent, mixed with electrolyte solution by Graphene colloidal solution, room temperature leaves standstill, and washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction process: 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, grinding; and use organic solvent ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C.
Of the present invention can the method for the few layer graphene powder of mass 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 again, reaction 1-2 hour, be warming up to 35 DEG C of reaction 30-50 minute, add deionized water 0.75-1.5L afterwards, 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 pickling and the washing of washing alternating centrifugal, 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: with electrolyte solution for 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 superjacent, washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction process: 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, grinding; and use organic solvent ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C.
Of the present invention can the method for the few layer graphene powder of mass preparation, the ionogen adopted 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 the method for the few layer graphene powder of mass preparation, organic solvent is alcohols, ketone, aldehydes organic solvent.
Of the present invention can the method for the few layer graphene powder of mass preparation, the number of plies of the graphene powder of the hydrazine hydrate reduction of preparation is 2-5 layer, 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.
Of the present invention can the method for the few layer graphene powder of mass 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, and carbon-to-oxygen ratio is 86.72, and 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, a large amount of reunions of reduced graphene self can be prevented; Adopt acid, alkali, salt electrolyte solution to be the floating reagent of solidifying wadding in the present invention, be convenient to the quick wash of Graphene, simple to operate, be beneficial to batch production, there are the bright prospects of heavy industrialization application; All have employed the solution of dilute concentration in the present invention, whole reaction process is very little on the impact of environment, and only containing a small amount of ion in waste liquid, processing cost is low, the sheet number of plies that the present invention's hydrazine hydrate reduction obtains graphene powder is 2-5 layer, 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; Be 3-7 layer by the sheet number of plies of the graphene powder obtained after hydrazine hydrate reduction again thermal treatment, good crystallinity, carbon-to-oxygen ratio is 86.72, and specific surface area is 271-393 m
2/ g, specific conductivity is 1741-2766 S/m.
(4) accompanying drawing explanation
Accompanying drawing 1 is the Raman spectrogram (Raman) of the Graphene obtained after hydrazine hydrate reduction and the reduction treatment of hydrazine hydrate reduction reheating;
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 is the X X-ray photoelectron spectroscopy X figure (XPS) that the reduction treatment of hydrazine hydrate reduction reheating obtains the 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 elevation carrection figure (b) of the Graphene of Graphene for hydrazine hydrate reduction; The thickness of Graphene is 1.109 nm;
Accompanying drawing 7 is the transmission electron microscope picture (TEM) that the reduction treatment of hydrazine hydrate reduction reheating obtains Graphene;
Accompanying drawing 8 is the scanning electron microscope (SEM) photograph (SEM) that the reduction treatment of hydrazine hydrate reduction reheating obtains 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 deionized water 0.75L afterwards, 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, adopt sulphuric acid soln and the deionized water alternating centrifugal of 5%, 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, 2L deionized water is added in the graphene oxide solution of 2L 0.5mg/mL, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add 7mL ammoniacal liquor (massfraction 28%) again, 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: with the sulphuric acid soln of massfraction 5% for solidifying wadding leafing agent, the sulphuric acid soln of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 0.5 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is 2-5 layer, carbon-to-oxygen ratio is 11.90, and specific surface area is about 242.4m
2/ g, specific conductivity about 225.7 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1000 DEG C of insulations 30 minutes, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, 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 about 309.4 m
2/ g, specific conductivity about 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: with the hydrochloric acid soln of massfraction 5% for solidifying wadding leafing agent, the hydrochloric acid soln of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, removing chlorion, wash the graphene powder that lyophilize obtains hydrazine hydrate reduction again, specific surface area about 346.1 m
2/ g, specific conductivity about 370.7 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 1 hour, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 350.1 m
2/ g, specific conductivity about 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: with the sodium hydroxide solution of massfraction 5% for solidifying wadding leafing agent, the sodium hydroxide solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 270.1 m
2/ g, specific conductivity about 168.1 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 273.4 m
2/ g, specific conductivity about 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: with the potassium hydroxide solution of massfraction 5% for solidifying wadding leafing agent, the potassium hydroxide solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 301.3 m
2/ g, specific conductivity about 355.8 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1000 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 393.7 m
2/ g, specific conductivity about 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: with the sodium nitrate solution of massfraction 5% for solidifying wadding leafing agent, the sodium nitrate solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 2 hours, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 271.2 m
2/ g, specific conductivity about 353.5 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 318.3 m
2/ g, specific conductivity about 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: with the metabisulfite solution of massfraction 5% for solidifying wadding leafing agent, the metabisulfite solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, removing sulfate ion, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 271.1 m
2/ g, specific conductivity about 214.0 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 319.3 m
2/ g, specific conductivity about 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: with the sodium chloride solution of massfraction 5% for solidifying wadding leafing agent, the sodium chloride solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, removing chlorion, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 232.8 m
2/ g, specific conductivity about 266.1 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 288.8 m
2/ g, specific conductivity about 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: with the sodium carbonate solution of massfraction 5% for solidifying wadding leafing agent, the sodium carbonate solution of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 257.2 m
2/ g, specific conductivity about 403.9 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 2 minutes, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 271.1 m
2/ g, specific conductivity about 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: with the sal volatile of massfraction 5% for solidifying wadding leafing agent, the sal volatile of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 1 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, to pH=7, lyophilize obtains the graphene powder of hydrazine hydrate reduction again, specific surface area about 260.7 m
2/ g, specific conductivity about 100.2 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 10 DEG C/min, 1050 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and with alcohol or acetone ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C, specific surface area about 272.8 m
2/ g, specific conductivity about 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 deionized water 1.5L afterwards, 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, adopt sulphuric acid soln and the deionized water alternating centrifugal of 5%, 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, 2L deionized water is added in the graphene oxide solution of 2L 0.5mg/mL, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add 7mL ammoniacal liquor (massfraction 28%) again, 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: with the sulphuric acid soln of massfraction 5% for solidifying wadding leafing agent, the sulphuric acid soln of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (-25 DEG C) leaves standstill 0.5 hour, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is 3 layers, carbon-to-oxygen ratio is 11.90, and specific surface area is about 240m
2/ g, specific conductivity about 230 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 2 DEG C/min, 1025 DEG C of insulations 2 hours, is cooled to room temperature.Afterwards, grinding, and use alcohol ultrasonic disperse, 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 about 312.3 m
2/ g, specific conductivity about 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 deionized water 1.1L afterwards, 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, adopt sulphuric acid soln and the deionized water alternating centrifugal of 5%, 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, 2L deionized water is added in the graphene oxide solution of 2L 0.5mg/mL, under agitation add 1.4 mL hydrazine hydrates (massfraction 50%), add 7mL ammoniacal liquor (massfraction 28%) again, 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: with the sulphuric acid soln of massfraction 5% for solidifying wadding leafing agent, the sulphuric acid soln of the Graphene colloidal solution of 1 volume with 2 volumes 5% is mixed, room temperature (30 DEG C) leaves standstill 2 hours, Graphene is slowly assembled, swim in superjacent, with the washing of deionization suction filtration, lyophilize obtains the graphene powder of hydrazine hydrate reduction, its number of plies is 4 layers, carbon-to-oxygen ratio is 11.90, and specific surface area is about 245m
2/ g, specific conductivity about 250.4 S/m.
(4) thermal reduction process: the Graphene of dried hydrazine hydrate reduction is put into tube furnace, under nitrogen protection, heats up with the temperature rise rate of 5 DEG C/min, 1025 DEG C of insulations 3 hours, is cooled to room temperature.Afterwards, grinding, and use formaldehyde ultrasonic disperse, 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 about 316.7 m
2/ g, specific conductivity about 1864.1 S/m.
The present invention is in the process of few layer (less than the 10 layers) Graphene of preparation, and the floating reagent of solidifying wadding used 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 for the present embodiment 1, be analyzed as follows:
Fig. 1 is the Raman spectrogram of the Graphene obtained after hydrazine hydrate reduction and the reduction treatment of hydrazine hydrate reduction reheating, D and the G peak in figure illustrates that sample prepared by two kinds of methods is all crystallinity layer graphene less 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 is the X X-ray photoelectron spectroscopy X figure (XPS) that the reduction treatment of hydrazine hydrate reduction reheating obtains the 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, containing a large amount of micro-nano thin slices in graphene powder;
Fig. 6 is elevation carrection figure (b) that hydrazine hydrate reduction obtains the Graphene of Graphene; The thickness of Graphene is 1.109 nm;
Accompanying drawing 7 is the transmission electron microscope picture (TEM) that the reduction treatment of hydrazine hydrate reduction reheating obtains Graphene, and this kind of Graphene exists a lot of gauffer after sintering;
Accompanying drawing 8 is the scanning electron microscope (SEM) photograph (SEM) that the reduction treatment of hydrazine hydrate reduction reheating obtains Graphene, illustrates that this kind of Graphene is made up of micro-nano of many puffy.
Claims (6)
1. can prepare the method lacking layer graphene powder by mass, it is characterized in that: the floating reagent of solidifying wadding making Graphene colloidal solution with various ionogen, makes Graphene float on superjacent fast, prepare graphene powder,
The method lacking layer graphene powder can be prepared by mass, 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, deionized water is added after reaction, keep 20-30 minute at 90-100 DEG C, then add hydrogen peroxide and deionized water, obtain glassy yellow graphite oxide solution; Afterwards, adopt pickling and the washing of washing alternating centrifugal, 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: with electrolyte solution for solidifying wadding leafing agent, mixed with electrolyte solution by Graphene colloidal solution, room temperature leaves standstill, and washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction process: 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, grinding; and use organic solvent ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C.
2. according to claim 1 can the method for the few layer graphene powder of mass 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 again, reaction 1-2 hour, be warming up to 35 DEG C of reaction 30-50 minute, add deionized water 0.75-1.5L afterwards, 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 pickling and the washing of washing alternating centrifugal, 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: with electrolyte solution for 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 superjacent, washing lyophilize obtains the graphene powder of hydrazine hydrate reduction;
(4) thermal reduction process: 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, grinding; and use organic solvent ultrasonic disperse, dry to obtain graphene powder for 50-60 DEG C.
3. according to claim 1 and 2 can the method for the few layer graphene powder of mass 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 or volatile salt, the massfraction concentration of the electrolyte solution of employing is 5%.
4. according to claim 1 and 2 can the method for the few layer graphene powder of mass preparation, it is characterized in that: organic solvent is alcohols, ketone or aldehydes organic solvent.
5. according to claim 1 and 2 can the method for the few layer graphene powder of mass 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, 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.
6. according to claim 1 and 2 can the method for the few layer graphene powder of mass 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, and specific surface area is 271-393 m
2/ g, specific conductivity is 1741-2766 S/m.
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| CN112678831B (en) * | 2021-02-02 | 2022-06-07 | 福建省三明正元化工有限公司 | Method for preparing silicon dioxide by using graphene oxide waste liquid |
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