CN108622886A - A kind of liquid nitrogen auxiliary prepares the method for high-quality graphene and high-quality graphene obtained - Google Patents
A kind of liquid nitrogen auxiliary prepares the method for high-quality graphene and high-quality graphene obtained Download PDFInfo
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
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Abstract
The present invention relates to a kind of liquid nitrogen auxiliary to prepare the method for high-quality graphene and high-quality graphene obtained, and graphene of the invention has the characteristics that oxygen content is low, defect is few, few layer graphene (being less than 5 layers) content is high and big with two-dimensional slice size.The present invention method be：Quasiflake graphite is placed in liquid nitrogen, high-speed stirred, makes liquid nitrogen volatilization to get to graphene powder after the completion of to be mixed.The method of the present invention rapidly and efficiently, safety and environmental protection and at low cost, and obtained graphene is high-quality, oxygen content is below 8%, and in the Raman spectrum of the graphene, the peak intensity ratio at the peaks D and the peaks G is below 0.8, for the peak intensity ratio at the peaks 2D and the peaks G 0.2 or more, method of the invention can be applied to the production of extensive high-quality graphene.
Description
Technical field
The invention belongs to carbon material technical field, it is related to a kind of graphene and preparation method thereof, especially a kind of high quality
Graphene and preparation method thereof, more particularly it relates to a kind of liquid nitrogen auxiliary prepare high-quality graphene method and
High-quality graphene obtained.
Background technology
Graphene is carbon atom with sp2The hexagonal honeycomb two-dimensional structure material that hybridized orbit is formed, has many excellent
Characteristic.There is graphene light transmittance, high thermal conductivity coefficient, high electron mobility, high conductivity, the room-temperature quantum Hall of superelevation to imitate
It answers, regulatable band gap, excellent mechanical property, efficient hydrogen storage property, unusual magnetism characteristic and perfect charge
Between interact.Just because of its these impayable characteristics, graphene is considered as next-generation microelectronic component, organic
The preferred material in the fields such as photoelectric material, high-efficiency energy-storage material, multifunctional composite and biomaterial.But high quality stone
The inexpensive magnanimity preparation of black alkene still faces awkward situation, greatly limits its development and application.
Up to the present, the preparation method of graphene is varied, can be divided mainly into method from top to bottom and oneself according to thinking
Lower and upper method two major classes.The former is by reacting to form covalent bond by small-molecule chemical, building the bi-dimensional cellular shape of graphene
Structure；The latter is to prepare two-dimensional graphene by removing three-dimensional block graphite material.It is more representational have CVD method,
SiC epitaxial growth methods, oxidation-reduction method, mechanical stripping method, the methods of liquid phase stripping method.
In these methods, the graphene quality that prepared by Part Methods is high but expensive, complicated for operation；Part Methods
It is easy to operate, but the graphene prepared is second-rate.So there is still a need for easy to operate, it is of low cost, it can quickly prepare height
The method of quality graphene is studied.
Invention content
For problems of the prior art, the purpose of the present invention is to provide a kind of high-quality graphene and its preparations
Method, this invention address that providing the graphene of a kind of (low oxygen content, the low defect) of high quality.
In addition, this invention address that offer is a kind of to be used to prepare stone especially by economic, efficient and low-risk process
The method of black alkene, the graphene have very high quality.
" high-quality graphene " of the present invention refers to：The oxygen content of the graphene 8% hereinafter, and the graphene drawing
In graceful spectrum, the peak intensity at the peaks D and the peaks G than 0.8 hereinafter, the peak intensity ratio at the peaks 2D and the peaks G is 0.2 or more.
Not only oxygen content is low, defect is few, the number of plies is few and has the characteristics that two-dimensional slice size is big for the graphene of the present invention, this
In the graphene of invention, the mass content of few layer graphene (number of plies is less than 5) in 10%-15%, for example, 10%, 11%,
11.5%, 12%, 13%, 13.5%, 14%, 14.3%, 14.6% or 15% etc..
" few layer graphene " of the present invention refers to its number of plies and is less than 5.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of method that liquid nitrogen auxiliary prepares graphene, especially a kind of liquid nitrogen auxiliary system
The method of standby high-quality graphene, the method includes：
Quasiflake graphite is placed in liquid nitrogen, is stirred, so that liquid nitrogen is volatilized after the completion of to be mixed, obtains graphene powder.
In the present invention, it is to stand that remaining liquid nitrogen is made to volatilize naturally to allow the mode that liquid nitrogen volatilizees, and can also heat makes to remain
Extraction raffinate nitrogen is evaporated, but is not limited to above two mode, other modes that liquid nitrogen can be made to volatilize can also be used for the present invention.
Preferably, relative to every 1g quasiflake graphites, the dosage of the liquid nitrogen is 100ml-800ml, for example, 100ml,
200ml、225ml、250ml、300ml、350ml、400ml、450ml、500ml、550ml、600ml、650ml、700ml、
750ml, 780ml or 800ml etc., preferably 400ml.
Preferably, the rotating speed of the stirring is 2000r/min-25000r/min, for example, 2000r/min, 4000r/
min、6000r/min、8000r/min、10000r/min、12500r/min、15000r/min、17000r/min、18500r/
Min, 20000r/min, 21000r/min, 22000r/min, 23000r/min, 24000r/min or 25000r/min etc., preferably
For 8000r/min-20000r/min, further preferably 20000r/min.
Preferably, the time of the stirring be 5min-60min, for example, 5min, 10min, 15min, 20min, 25min,
28min, 30min, 35min, 40min, 42min, 45min, 50min, 55min or 60min etc..
As the optimal technical scheme of the method for the invention, due to stirring during liquid nitrogen volatilize, preferably exist
Liquid nitrogen is constantly filled into during stirring, relative to 1g quasiflake graphites after keeping benefit complete, the total amount of liquid nitrogen is in 100ml-
800ml。
Preferably, the amount of the liquid nitrogen filled into is equal with the amount of the liquid nitrogen vapored away in whipping process.
Preferably, the equipment used that stirs is high speed machine blender.
Preferably, during being stirred using high speed machine blender, stirring cutter root diameter is not less than 16mm,
Preferably 32mm.
Preferably, during being stirred using high speed machine blender, stirring cutter stator rotor gap is not more than
1mm, preferably 0.5mm.
As the optimal technical scheme of the method for the invention, the quasiflake graphite is prepared via a method which to obtain：
Intercalation first is carried out to graphite raw material, then heating makes the graphite raw material after intercalation expand, and obtains quasiflake graphite.
Preferably, the volume for the quasiflake graphite being transformed into from every 1g graphite raw materials is 300ml-600ml, for example,
300ml, 350ml, 400ml, 450ml, 500ml, 520ml, 550ml, 575ml or 600ml etc..
Preferably, the graphite raw material includes that crystalline flake graphite, graphite powder, expanded graphite, fullerene, carbon nanotube, carbon are received
In rice band, carbon black, mesoporous carbon or activated carbon any one or at least two combination, but be not limited to the above-mentioned object enumerated
Matter, other graphite raw materials commonly used in the art can also be used for the present invention.
Preferably, the intercalator that the intercalation uses is any one in acid, alkali metal, alkaline-earth metal or salt, excellent
It is selected as acid.
Preferably, the mode of the heating is：Heat any one in stove heat or microwave heating or at least two
Combination, preferably microwave heating.
It is highly preferred that the quasiflake graphite is prepared via a method which to obtain：
(1) intercalation is carried out to graphite raw material using acid, obtains the graphite raw material of intercalation；
(2) microwave radiation is carried out to the graphite raw material of intercalation under inert gas protection, obtains quasiflake graphite.
The quasiflake graphite being prepared by this optimal technical scheme is fluffy quasiflake graphite, from every 1g graphite original
Expect that the volume that the quasiflake graphite being transformed into occurs is 300ml-600ml.
Preferably, during step (1) prepares the graphite raw material of intercalation, graphite raw material is placed in acid solution, is stirred, Gu
Liquid detaches, and obtains the graphite raw material of intercalation.
Preferably, the sulphur that the mass fraction of the acid solution is 30%-72% perchloric acid, mass fraction are 50%-98%
Sour, mass fraction is the mixture of any one or at least two in the nitric acid of 50%-98%, preferably 72% high chlorine
In acid, 98% sulfuric acid or 98% nitric acid any one or at least two mixture, further preferably 72% height
Chloric acid, or the mixture for 98% sulfuric acid and 98% nitric acid.
In the present invention, the mass fraction is the perchloric acid of 30%-72%, mass fraction is, for example, 30%, 33%,
35%, 37.5%, 40%, 43%, 46%, 50%, 52%, 55%, 58%, 60%, 65%, 68%, 70% or 72% etc., it is excellent
It is selected as 72%.
In the present invention, the mass fraction is the sulfuric acid of 50%-98%, mass fraction is, for example, 50%, 55%, 58%,
60%, 63%, 65%, 70%, 72%, 76%, 78%, 82%, 85%, 90%, 92%, 94%, 96% or 98% etc..
In the present invention, the mass fraction is the nitric acid of 50%-98%, mass fraction is, for example, 50%, 53%, 58%,
60%, 65%, 66%, 68%, 70%, 73%, 75%, 77%, 78%, 80%, 84%, 88%, 90%, 93%, 96% or
98% etc..
Preferably, the time of the stirring be 1min-36h, for example, 1min, 2min, 3min, 5min, 8min, 10min,
12min、15min、20min、25min、28min、0.5h、0.8h、1h、2h、3h、4h、5h、7h、10h、12h、15h、17h、
18h, 20h, for 24 hours, 25h, 27h, 30h, 32h, 34h, 35h or 36h etc..For different acid solutions, preferred mixing time is different,
For example, when acid solution is the perchloric acid that mass fraction is 30%-72%, preferred mixing time is 1min-5min；When acid solution is
The mixing of any one or two kinds in the nitric acid that the sulfuric acid or mass fraction that mass fraction is 50%-98% are 50%-98%
When object, preferred mixing time is 12h-36h.
Stirring of the present invention carries out at room temperature.
In the present invention, the amount for the acid solution that step (1) uses is without clearly limiting, as long as meeting can be such that graphite raw material soaks completely
Not in acid solution.
As the optimal technical scheme of the method for the invention, the acid solution is the perchloric acid that mass fraction is 72%, and
Relative to 1g graphite raw materials, the dosage of the acid solution is 100ml, and the time of the stirring is 3min.
As the optimal technical scheme of the method for the invention, the acid solution be the sulfuric acid that mass fraction is 98% and/or
The nitric acid that mass fraction is 98%, and relative to 1g graphite raw materials, the dosage of the acid solution is 25ml-60ml, the stirring
Time is 12h-36h.
In the present invention, " nitric acid that the sulfuric acid and/or mass fraction that mass fraction is 98% are 98% " refers to：Can be
The sulfuric acid that mass fraction is 98% can also be the nitric acid that mass fraction is 98%, can also be that mass fraction is 98% sulphur
The nitrate mixture that acid and mass fraction are 98%.
In the present invention, after step (1) has carried out intercalation step, the recyclable reuse of acid solution.
Preferably, step (2) described inert gas is any one in nitrogen, argon gas, helium, neon, Krypton or xenon
Kind or at least two combination, preferably any one in nitrogen or argon gas.
Preferably, the power of step (2) described microwave radiation be 100W-1200W, for example, 100W, 200W, 300W,
400W, 600W, 700W, 800W, 950W, 1000W, 1100W or 1200W etc., preferably 700W-1000W.
Preferably, the time of step (2) described microwave radiation be 10s-300s, for example, 10s, 20s, 30s, 40s, 45s,
50s、60s、65s、70s、80s、90s、100s、110s、130s、135s、150s、160s、180s、200s、215s、230s、
245s, 260s, 270s, 280s or 300s etc., preferably 90s-300s.
As the optimal technical scheme of the method for the invention, a method of graphene is prepared, is included the following steps：
(1) graphite raw material is placed in the perchloric acid that mass fraction is 72%, graphite raw material is made to be completely submerged in the quality
In the perchloric acid that score is 72%, 1min-5min is stirred, is separated by solid-liquid separation, obtains the graphite raw material of perchloric acid intercalation；
(2) under the protection of nitrogen, the microwave radiation of 180s-300s is carried out to the graphite raw material of perchloric acid intercalation, is obtained
Quasiflake graphite；
(3) according to the dosage standard of 1g quasiflake graphites/(400ml-600ml) liquid nitrogen, quasiflake graphite is placed in liquid nitrogen
In, stir 5min-60min, the liquid for the liquid nitrogen equivalent for constantly filling into and vaporing away in whipping process using high speed machine blender
Nitrogen, being stood after the completion of stirring makes liquid nitrogen volatilize naturally, obtains graphene powder.
As the another optimal technical scheme of the method for the invention, a method of preparing graphene, including following step
Suddenly：
(1) graphite raw material is placed in the nitric acid that mass fraction is 98% and/or the sulfuric acid that mass fraction is 98%, makes stone
Black raw material is completely submerged in the sulfuric acid that the nitric acid that the mass fraction is 98% and/or mass fraction are 98%, stirs 12h-
36h is separated by solid-liquid separation, obtains the graphite raw material of intercalation；
(2) under the protection of argon gas, the microwave radiation of 180s-300s is carried out to the graphite raw material of intercalation, obtains vermiform
Graphite；
(3) according to the dosage standard of 1g quasiflake graphites/(400ml-600ml) liquid nitrogen, quasiflake graphite is placed in liquid nitrogen
In, stir 5min-60min, the liquid for the liquid nitrogen equivalent for constantly filling into and vaporing away in whipping process using high speed machine blender
Nitrogen, being stood after the completion of stirring makes liquid nitrogen volatilize naturally, obtains graphene powder.
Second aspect, the present invention provide the graphene that method as described in relation to the first aspect is prepared, the graphene
The average-size of two dimensional surface at 2 μm -5 μm, for example, 2 μm, 2.5 μm, 3 μm, 3.2 μm, 3.4 μm, 3.5 μm, 3.8 μm, 4 μm,
4.3 μm, 4.5 μm, 4.7 μm or 5 μm etc..
In the present invention, " average-size of the two dimensional surface of graphene " refers to：Cross all directions at the center of two dimensional surface
Size average value.
Preferably, the graphene have 8% or less even lower oxygen content, for example, 8%, 7.5%, 7%,
6.5%, 6%, 5% or 4% etc., preferably 5% or less.
In the present invention, in the Raman spectrum of graphene, the peak intensity ratio (I at the peaks D and the peaks GD/IG) 0.8 hereinafter, be, for example,
0.8,0.75,0.7,0.6,0.55,0.5,0.4,0.3 or 0.2 etc., preferably 0.5 are hereinafter, further preferably 0.2.The present invention
Graphene ID/IGIt is high-quality 0.8 hereinafter, illustrating that its defect is few.
In the present invention, in the Raman spectrum of graphene, the peak intensity ratio at the peaks 2D and the peaks G 0.2 or more, for example, 0.2,0.3,
0.4 or 0.8 etc., preferably 0.5 or more, further preferably 0.8.
The peaks G of graphene, are the peaks usually shown in the material based on graphite, are shown in about 1500cm-1To about
1700cm-1Range.The peaks G are to vibrate have E in the opposite direction by hexagonal carbon atom and adjacent atom2g
The pattern of symmetry causes, and wherein the vibration mode is the situation of the Raman permission of the permitted Raman scattering of the symmetry, this
It can be observed in primary scattering.Under normal circumstances, when the number of graphene layer is smaller, weak intensity can be observed.
The peaks D of graphene are them by A1' vibration mode causes, in this mode hexagonal carbon atom with towards the carbon original
The atom of son vibrates in the opposite direction, is in about 1250cm-1To about 1450cm-1Peak shown in range.Due to pair of Raman scattering
Title property, does not observe this A in the lattice structure of intact monolayer graphene1' vibration mode, and work as and occur in hexagonal structure
When defect, or when the marginal portion of graphene is externally exposed, the A is observed1' vibration mode.
The peaks 2D of graphene are them by above-mentioned A1' vibration mode in, release two photons rescattering cause,
In about 2600cm-1To about 2800cm-1The peak that shows of range.Due to generating two resonance in scattering process so that should
Scattering refers to double resonance Raman scattering, and due to the effect of the resonance, which is significantly shown in spectrum.
Particularly, the peaks 2D are entirely different between single-layer graphene and multi-layer graphene.In single-layer graphene, institute
Peak is stated with Lorenz linear, i.e., narrow width and high intensity；Meanwhile in two layers or more of graphene, multiple peaks weigh each other
It folds and has broad peak, and therefore, single-layer graphene can be distinguished by the shape at peak.
The method of graphene is prepared in the present invention, graphene is stripping and micronized from graphite so that with shelling
From the quantity of graphene layer reduce, the intensity at the peaks G becomes smaller, and the intensity at the peaks 2D increases.Therefore, as graphene is effective
Ground is removed from graphite, I2D/IGValue increases, and the relative extent of the stripping of graphene can be evaluated by using the value,
I2D/IGHigher, the effect of stripping is better, and the mass content for the few layer graphene removed is higher.
The I of general commercialization graphene2D/IGValue is about 0.1 to about 0.15；And the I of the graphene of the present invention2D/IGSignificantly
Be increased to about 0.2 or bigger, which means that the present invention graphene more effectively removed compared to commercial graphite alkene so that
Graphene in few layer state has high content, and in graphene of the invention, the quality of few layer graphene (being less than 5 layers) contains
Amount is in 10%-15%.
Compared with the prior art, the present invention has the advantages that：
(1) the present invention provides a kind of is assisted using liquid nitrogen rapidly and efficiently, economy, safety and environmental protection and low-risk to prepare
The method of high-quality graphene, the method is very simple, only quasiflake graphite need to be placed in liquid nitrogen, high-speed stirred, then
Make liquid nitrogen vaporization, can obtain the high-quality graphene powder that oxygen content is low, defect is few, the number of plies is few, method of the invention can be with
Production applied to extensive high-quality graphene.
(2) graphene is prepared using liquid nitrogen auxiliary, after the completion of high-speed stirred, liquid nitrogen vaporization can be direct in method of the invention
The graphene powder of high-purity is obtained, eliminates and needs the post-processing steps such as washing, dry, the present invention in the method for the prior art
Method it is easier, be suitble to industrialized production.
(3) average-size of the two dimensional surface of graphene of the invention is at 2 μm -5 μm, and oxygen content is 8% hereinafter, and described
In the Raman spectrum of graphene, the peak intensity at the peaks D and the peaks G than 0.8 hereinafter, the peak intensity ratio at the peaks 2D and the peaks G is 0.2 or more, few layer
The mass content of graphene (being less than 5 layers) is in 10%-15%.
Description of the drawings
Fig. 1 is that embodiment 1 obtains the high-resolution-ration transmission electric-lens photo of graphene；
Fig. 2 is the stereoscan photograph for the graphene that embodiment 1 obtains；
Fig. 3 is that embodiment 1 obtains the Raman scattering collection of illustrative plates of graphene；
Fig. 4 is the X ray diffracting spectrum for the graphene that embodiment 1 obtains.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
The present invention will be described in detail by way of examples below, but the present invention is not limited in following embodiments.
Following embodiment and comparative example measure the microcosmic knot of graphene using transmission electron microscope (20 S-TWIN of Tecnai G2)
Structure.
Following embodiment and comparative example measure the type looks of graphene using scanning electron microscope (Hitachi S4800+EDS).
Following embodiment and comparative example measure graphene carbon oxygen element content using elemental analyser, to obtain graphene
Oxygen content.
Following embodiment and comparative example measure graphene using laser Raman spectrometer (Renishaw inVia plus)
Structure.
Following embodiment and comparative example measure the structure of graphene using X-ray diffractometer (D/MAX-TTRIII (CBO)).
Embodiment 1
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 3min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 600ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/mi, liquid nitrogen is continuously replenished during stirring in time 20min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 6.8 weight %, ID/IGIt is 0.25, I2D/IGIt is 0.6, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Fig. 1 be embodiment 1 obtain the transmission electron microscope photo of graphene, as seen from the figure, the graphene removed compared with
Thin, the number of plies is less.
Fig. 2 is the stereoscan photograph for the graphene that embodiment 1 obtains, as seen from the figure, the graphene removed
Two dimensional surface average-size at 2 μm -5 μm.
Fig. 3 is that embodiment 1 obtains the Raman scattering collection of illustrative plates of graphene, as seen from the figure, ID/IGIt is 0.25, illustrates to remove
Obtained graphene defect is less；I2D/IGIt is 0.6, illustrates that the graphene number of plies that stripping obtains is less.
Fig. 4 is the X ray diffracting spectrum for the graphene that embodiment 1 obtains, and as seen from the figure, diffracting spectrum is not apparent
Graphite peaks, illustrate that peeling effect is preferable.
Embodiment 2
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter to the 50ml concentrated sulfuric acids (be purchased from Beijing Chemical Plant, quality mass concentration be 98%) in, stir 2 days at room temperature, filtering.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 320ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/min, liquid nitrogen is continuously replenished during stirring in time 20min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 8.0 weight %, ID/IGIt is 0.4, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 3
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml concentrated nitric acids and concentrated sulfuric acid nitration mixture that (concentrated nitric acid is 3 with concentrated sulfuric acid volume ratio:2, concentrated nitric acid is purchased from Beijing Chemical Plant,
Mass concentration is 98%, and the concentrated sulfuric acid is purchased from Beijing Chemical Plant, mass concentration 98%) in, it stirs 2 days at room temperature, filtering.
The graphite being obtained by filtration is placed in corundum crucible, nitrogen is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 480ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/min, liquid nitrogen is continuously replenished during stirring in time 20min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 6.8 weight %, ID/IGIt is 0.5, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 4
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 3min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 1.5min takes out after cooling, obtains the fluffy quasiflake graphites of 450ml.
The quasiflake graphite that microwave obtains is placed in 500ml beakers, 400ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/min, liquid nitrogen is continuously replenished during stirring in time 20min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 7.2 weight %, ID/IGIt is 0.4, I2D/IGIt is 0.6, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 5
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 3min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 600ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 10000r/min, liquid nitrogen is continuously replenished during stirring in time 30min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 7.0 weight %, ID/IGIt is 0.5, I2D/IGIt is 0.6, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 6
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
1g graphite powders (being purchased from AlfaAesar companies, -20 to+80 mesh, purity is 99 weight %, same as below) are added
Into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), 3min is stirred at room temperature, is filtered.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 520ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/min, liquid nitrogen is continuously replenished during stirring in time 30min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 7.5 weight %, ID/IGIt is 0.5, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 7
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 3min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 600ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 15000r/min, liquid nitrogen is continuously replenished during stirring in time 60min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 6.3 weight %, ID/IGIt is 0.3, I2D/IGIt is 0.6, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 8
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 3min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 600ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 600ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 8000r/min, liquid nitrogen is continuously replenished during stirring in time 60min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 6.4 weight %, ID/IGIt is 0.3, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 9
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml perchloric acid (being purchased from Beijing Chemical Plant, mass concentration 72%), stir 5min at room temperature, filters.
The graphite being obtained by filtration is placed in corundum crucible, argon gas is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 5min takes out after cooling, obtains the fluffy quasiflake graphites of 600ml.
The quasiflake graphite that microwave obtains is placed in 500ml beakers, 200ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 8000r/min, liquid nitrogen is continuously replenished during stirring in time 60min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 7.8 weight %, ID/IGIt is 0.5, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Embodiment 10
The present embodiment is for illustrating that liquid nitrogen auxiliary prepares high-quality graphene.
By 1g flaky graphites (being purchased from Sigma-Aldrich companies, 50 mesh, purity is 99 weight %, same as below) plus
Enter into 50ml concentrated nitric acids and concentrated sulfuric acid nitration mixture that (concentrated nitric acid is 3 with concentrated sulfuric acid volume ratio:2, concentrated nitric acid is purchased from Beijing Chemical Plant,
Mass concentration is 98%, and the concentrated sulfuric acid is purchased from Beijing Chemical Plant, mass concentration 98%) in, it stirs 2 days at room temperature, filtering.
The graphite being obtained by filtration is placed in corundum crucible, nitrogen is filled with and is sealed.Crucible is placed in micro-wave oven (Glanz
Household microwave oven, 700W power) in, microwave 3min takes out after cooling, obtains the fluffy quasiflake graphites of 480ml.
The quasiflake graphite that microwave obtains is placed in 1000ml beakers, 800ml liquid nitrogen is added, uses high speed machine immediately
Blender is stirred (instrument is purchased from IKA, and 18 digital ULTRA-TURRAX, S 18N-19G of T disperse cutter head).Rotating speed
It is set as 18000r/min, liquid nitrogen is continuously replenished during stirring in time 40min.After the completion of stirring, wait for that liquid nitrogen volatilization is complete
Obtain graphene powder.
After measured, the graphene oxygen content that prepared by this method is 7.7 weight %, ID/IGIt is 0.4, I2D/IGIt is 0.5, graphite
The average-size of the two dimensional surface of alkene is at 2 μm -5 μm.
Comparative example 1
Outside the step for replacing with deionized water, and be filtered and dry after completion of stirring liquid nitrogen, other preparations
Method and condition is same as in Example 10.
After measured, the graphene oxygen content that prepared by this method is 8.0 weight %, ID/IGIt is 1.0, I2D/IGIt is 0.2, graphite
The average-size of the two dimensional surface of alkene is in 100nm-600nm.
Comparative example 2
Outside the step for replacing with ethyl alcohol, and be filtered, wash and dry after completion of stirring liquid nitrogen, other preparations
Method and condition is same as in Example 10.
After measured, the graphene oxygen content that prepared by this method is 7.8 weight %, ID/IGIt is 1.2, I2D/IGIt is 0.1, graphite
The average-size of the two dimensional surface of alkene is in 50nm-200nm.
By comparative example 1 and comparative example 2 as can be seen that liquid nitrogen is replaced with deionized water or ethyl alcohol, cannot obtain big
Two-dimensional slice graphene, and ID/IGValue is significantly raised, I2D/IGValue is decreased obviously, and is illustrated that peeling effect is deteriorated, is lacked layer
Content of the content of graphene significantly lower than few layer graphene in the graphene of the present invention.Moreover, using the scheme of water or ethyl alcohol
It the post-processing steps such as being only filtered and dries, can just access graphene powder, the method relative to the present invention is more cumbersome,
It is unfavorable for industrialized production.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of method that liquid nitrogen auxiliary prepares graphene, which is characterized in that the described method comprises the following steps：
Quasiflake graphite is placed in liquid nitrogen, is stirred, so that liquid nitrogen is volatilized after the completion of to be mixed, obtains graphene powder.
2. according to the method described in claim 1, it is characterized in that, relative to every 1g quasiflake graphites, the dosage of the liquid nitrogen
For 100ml-800ml；
Preferably, relative to every 1g quasiflake graphites, the dosage of the liquid nitrogen is 400ml；
Preferably, the rotating speed of the stirring be 2000r/min-25000r/min, preferably 8000r/min-20000r/min, into
One step is preferably 20000r/min；
Preferably, the time of the stirring is 5min-60min；
Preferably, liquid nitrogen is constantly filled into during the stirring, made relative to every 1g quasiflake graphites, the total amount of liquid nitrogen exists
100ml-800ml；
Preferably, the amount of the liquid nitrogen filled into is equal with the amount of the liquid nitrogen vapored away in whipping process；
Preferably, the equipment used that stirs is high speed machine blender；
Preferably, during being stirred using high speed machine blender, stirring cutter root diameter is not less than 16mm, preferably
For 32mm；
Preferably, during being stirred using high speed machine blender, stirring cutter stator rotor gap is not more than 1mm,
Preferably 0.5mm.
3. method according to claim 1 or 2, which is characterized in that the quasiflake graphite is prepared via a method which
It arrives：Intercalation first is carried out to graphite raw material, then heating makes the graphite raw material after intercalation expand, and obtains quasiflake graphite；
Preferably, the volume for the quasiflake graphite being transformed into from every 1g graphite raw materials is 300ml-600ml.
4. according to the method described in claim 3, it is characterized in that, the graphite raw material includes crystalline flake graphite, graphite powder, expansion
In graphite, fullerene, carbon nanotube, carbon nanobelts, carbon black, mesoporous carbon or activated carbon any one or at least two group
It closes；
Preferably, the intercalator that the intercalation uses is any one in acid, alkali metal, alkaline-earth metal or salt, preferably
Acid；
Preferably, the mode of the heating is：Heat in stove heat or microwave heating any one or at least two combination,
Preferably microwave heating.
5. method according to claim 3 or 4, which is characterized in that the quasiflake graphite is prepared via a method which
It arrives：
(1) intercalation is carried out to graphite raw material using acid, obtains the graphite raw material of intercalation；
(2) microwave radiation is carried out to the graphite raw material of intercalation under inert gas protection, obtains quasiflake graphite.
6. according to the method described in claim 5, it is characterized in that, the process for the graphite raw material that step (1) prepares intercalation is：It will
Graphite raw material is placed in acid solution, is stirred, and is separated by solid-liquid separation, is obtained the graphite raw material of intercalation；
Preferably, the acid solution be mass fraction be 30%-72% perchloric acid, mass fraction be 50%-98% sulfuric acid, matter
Measure score be 50%-98% nitric acid in any one or at least two mixture, preferably 72% perchloric acid, 98%
Sulfuric acid or 98% nitric acid in any one or at least two mixture, further preferably 72% perchloric acid, or
For the mixture of 98% sulfuric acid and 98% nitric acid；
Preferably, the time of the stirring is 1min-36h；
Preferably, the acid solution is the perchloric acid that mass fraction is 72%, and relative to 1g graphite raw materials, the dosage of the acid solution
Time for 100ml, the stirring is 3min；
Preferably, the acid solution is the sulfuric acid that mass fraction is 98% and/or the nitric acid that mass fraction is 98%, and relative to 1g
The dosage of graphite raw material, the acid solution is 25ml-60ml, and the time of the stirring is 12h-36h.
7. method according to claim 5 or 6, which is characterized in that step (2) described inert gas is nitrogen, argon gas, helium
In gas, neon, Krypton or xenon any one or at least two combination, preferably any one in nitrogen or argon gas；
Preferably, the power of step (2) described microwave radiation is 100W-1200W, preferably 700W-1000W；
Preferably, the time of step (2) described microwave radiation is 10s-300s, preferably 90s-300s.
8. according to claim 1-7 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) graphite raw material is placed in the perchloric acid that mass fraction is 72%, graphite raw material is made to be completely submerged in the quality point
Number is separated by solid-liquid separation in 72% perchloric acid, to stir 1min-5min, obtains the graphite raw material of perchloric acid intercalation；
(2) under the protection of nitrogen, the microwave radiation of 180s-300s is carried out to the graphite raw material of perchloric acid intercalation, obtains worm
Shape graphite；
(3) according to the dosage standard of 1g quasiflake graphites/(400ml-600ml) liquid nitrogen, quasiflake graphite is placed in liquid nitrogen, is made
5min-60min is stirred with high speed machine blender, the liquid nitrogen for the liquid nitrogen equivalent for constantly filling into and vaporing away in whipping process stirs
Being stood after the completion of mixing makes liquid nitrogen volatilize naturally, obtains graphene powder.
9. according to claim 1-7 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) graphite raw material is placed in the nitric acid that mass fraction is 98% and/or the sulfuric acid that mass fraction is 98%, keeps graphite former
Material is completely submerged in the nitric acid that the mass fraction is 98% and/or the sulfuric acid that mass fraction is 98%, stirs 12h-36h,
It is separated by solid-liquid separation, obtains the graphite raw material of intercalation；
(2) under the protection of argon gas, the microwave radiation of 180s-300s is carried out to the graphite raw material of intercalation, obtains quasiflake graphite；
(3) according to the dosage standard of 1g quasiflake graphites/(400ml-600ml) liquid nitrogen, quasiflake graphite is placed in liquid nitrogen, is made
5min-60min is stirred with high speed machine blender, the liquid nitrogen for the liquid nitrogen equivalent for constantly filling into and vaporing away in whipping process stirs
Being stood after the completion of mixing makes liquid nitrogen volatilize naturally, obtains graphene powder.
10. the graphene being prepared such as any one of claim 1-9 the methods, which is characterized in that the two of the graphene
The average-size of dimensional plane is at 2 μm -5 μm；
Preferably, the oxygen content of the graphene 8% hereinafter, preferably 5% or less；
Preferably, in the Raman spectrum of the graphene, the peak intensity ratio at the peaks D and the peaks G 0.8 hereinafter, preferably 0.5 hereinafter, into
One step is preferably 0.2；
Preferably, in the Raman spectrum of the graphene, the peak intensity ratio at the peaks 2D and the peaks G in 0.2 or more, preferably 0.5 or more, into
One step is preferably 0.8；
Preferably, in the graphene, the mass content of few layer graphene of the number of plies less than 5 is in 10%-15%.
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