CN105800603B - A kind of quick method for preparing high-quality graphene - Google Patents
A kind of quick method for preparing high-quality graphene Download PDFInfo
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- CN105800603B CN105800603B CN201610255327.2A CN201610255327A CN105800603B CN 105800603 B CN105800603 B CN 105800603B CN 201610255327 A CN201610255327 A CN 201610255327A CN 105800603 B CN105800603 B CN 105800603B
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a kind of quick method for preparing high-quality graphene, graphite powder is realized into intercalation with the solid-state intercalator mixing and ball milling and suitably heating that can resolve into gas after being heated completely, then 100~1200W 0.05~10min of microwave radiation processing is carried out again, intercalator resolves into gas completely at high temperature, gas molecule penetrates into graphite flake layer and overcomes the Van der Waals force between graphite flake layer, reaches graphite and is effectively peeled off.The present invention is simple with preparation process, and manufacturing cost is cheap, and technological operation is convenient, rapidly and efficiently, green, and product quality is high, the advantage such as easy large-scale use.
Description
Technical field
The invention belongs to field of inorganic materials, and in particular to a kind of quick method for preparing high-quality graphene.
Background technology
Professor Geim from Univ Manchester UK in 2004 etc. is separated from graphite first using adhesive tape stripping method
Since graphene, graphene increasingly causes the extensive pass of researcher with its unique structure, property and potential application
Note, and have become the focus of the various fields research such as material, chemistry, physics.In recent years, scientific research personnel develops numerous systems
The method of standby graphene, wherein mainly including mechanical stripping method, chemical vapor deposition (CVD), epitaxial growth and oxidation-reduction method
Deng.Its controllability of mechanical stripping method is poor, and obtained graphene size is smaller and very big uncertainty be present, while efficiency
It is low, be not suitable for large-scale production.In order to overcome this shortcoming, the graphene film of large area can be successfully prepared by CVD, still
CVD treatment conditions are harsh, and operating process is more complicated, and energy expenditure is big and is not suitable for large-scale production.On the other hand, by outer
Epitaxial growth can prepare uniform graphene platelet in large area, but the major defect cost of this method is high, and need
To be carried out in high temperature.The most frequently used method that oxidation-reduction method is prepared as graphene, it is also considered as most promising use
In the method for industrial production graphene.However, this method is still having the problem of many on expanding production, control, production are such as reduced
Product purifying and environmental pollution etc..
Therefore, graphene that is how inexpensive, expeditiously quickly preparing high quality is still a study hotspot and problem.
In order to develop a kind of fast preparation method to realize the extensive preparation of graphene, researchers are by constantly testing spy
Rope, find by microwave radiation can with the warm-up movement of the oxy radical such as hydroxyl (- OH), carboxyl (- COOH) on induced oxidation graphite,
These oxygen-containing functional groups is decomposed, decompose and produce substantial amounts of micro-molecular gas, so as to overcome oxidized graphite flake interlayer
Van der Waals force, realize the quick stripping of oxidized graphite flake layer, obtain graphene.Chen etc. reports will be divided using microwave radiation
The graphene oxide that is dispersed in the mixed solution of DMF and water carry out quick thermal reduction obtain reduction graphene (Carbon,
2010,48(4):1146-1152)。
Due to the uniform heating advantage being rapidly heated of microwave radiation, it has been proposed as an efficient heating means
Graphene is prepared for quick, and the stripping preparation of graphene is effectively realized under the effect of some adjuvants.Janowska etc.
Report and be dispersed in using expanded graphite as presoma in ammonia spirit after being ultrasonically treated a period of time, then it is carried out micro-
Wave heating has synthesized graphene film (Nano Research, 2010,3 (2) of large stretch of few layer:126-137).
CN201310036671 discloses a kind of method that rapid thermal treatment prepares graphene in air atmosphere, and this method is using oxidation stone
After being mixed with nitrogen-containing compound, the graphene powder of N doping is prepared by microwave rapid thermal treatment as presoma for black alkene.Ye
Deng the graphite oxide (GO) and ammonium hydrogen carbonate prepared by the use of Hummers methods as presoma, under the conditions of Microwave-assisted firing, soon
Speed reduction prepares graphene (Carbon, 2012,50 (6) with stripping:2134-2140).These Microwave-assisted Reductions at present
Research is concentrated mainly on the graphite oxide for using pretreatment or graphene oxide and synthesized as presoma or by liquid phase ultrasound.This
The time is longer in a little preprocessing process, while is inevitably related to the use of a series of chemical reagent, is unfavorable for environment
Protection, and the graphene defect produced is relatively more, and its intrinsic property receives certain destruction, therefore to widen graphene
The effect of application, the quick preparation of intrinsic graphene need to be further realized by non-oxidation or weak oxide, to meet to industrialize
Production requirement.
The content of the invention
It is an object of the invention in place of overcome the deficiencies in the prior art, there is provided one kind quickly prepares high-quality graphene
Method, be not related to redox path, it is green, cost is cheap, simple to operate, rapidly and efficiently, obtained graphene knot
Structure is complete, defect is less, oxygen content is low, is adapted to large-scale promotion.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of quick method for preparing high-quality graphene, including：
1) using graphite powder as raw material, according to the quality of graphite powder and the solid-state intercalator that gas can be resolved into after being heated completely
Than for 1:1~1:40 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into ball grinder, according to ratio of grinding media to material 6~20:1 adds size not
One mill ball, and 1/3~2/3 that the cumulative volume of total charge i.e. mixture and mill ball is ball milling tank volume is controlled, with
80~120r/min rotating speed 0.25~2h of stirring ball-milling, edge defect is produced by ball milling graphite powder, is easy to intercalator
In embedded graphite powder, the two is realized mixing intercalation, intercalator physics intercalated graphite mixture is obtained, in uniform black solid
Mixture；Using mill ball not of uniform size, different size cooperates, can ball milling obtain the graphite powder that particle diameter differs, from
And graphite powder is produced the edge defect to differ, preferably mix intercalation so as to promote to realize in intercalator insertion graphite powder；City
The mill ball sold has combination not of uniform size；
3) the black solid mixture obtained in step 2) is placed in microwave equipment with 100~1200W power microwave
0.05~10min is heated, obtains solid graphite alkene.
Preferably, in the step 3), the black solid mixture obtained in step 2) is first placed in sealing reactor,
20min~6h is heated in the vacuum drying oven that temperature is 40~90 DEG C, takes out, after being cooled to room temperature, transfers to microwave equipment
In 0.05~10min heated with 100~1200W power microwave, can obtain in the case where not producing redox reaction
Solid graphite alkene.
Heated first under 40~90 DEG C of lower temperature, temperature does not include height, and intercalator will not be big under this temperature conditions
Amount is decomposed, and would not also be produced enough gas, can be prevented graphite from peeling off；Meanwhile certain temperature can promote molecule to transport
It is dynamic, further promote graphite powder to be realized with intercalator and effectively mix intercalation, obtain the intercalator physics intercalated graphite of high quality
Mixture；Heating can prevent a small amount of intercalator for resolving into gas from being lost because of gaseous volatilization in reactor is sealed, and treat
These decomposed intercalators can recover the solid state before decomposing again after cooling, so as to ensure the amount of intercalator and follow-up micro-
The peeling effect of ripple processing.
Promote intercalation in above-mentioned heating stepses and then coordinate microwave heating, microwave heating has relative to traditional heating
Temperature is uniform, temperature rises fast effect, and quick caused hot environment can make intercalator is thorough rapidly to decompose generation completely
A large amount of gases, along with expansion of the microwave to graphite so that intercalator decomposes obtained a large amount of gases point in a short time
Son can be rapidly permeated into graphite flake layer, and Height Impact power caused by a large amount of gases can overcome the model between graphite flake layer rapidly
De Huali, so as to realize graphite it is quick, completely strip, obtain in uniform large stretch of flake structure, and lamella effect is kept
Good structural integrity, defect are less, hypoxic high-quality graphene.
The power of the microwave is 100~1200W, and correspondingly, microwave heating time is 0.05~10min；Power is higher,
Heating rate is fast, and the heat time accordingly shortens, and intercalator can decompose completely in a short time produces a large amount of gases, caused punching
It is big to hit power, peeling effect and more efficient；Power is lower, and the heat time accordingly extends.The microwave equipment of use is, for example, microwave
Stove；The power of micro-wave oven may be referred to micro-wave oven specification and be converted.
In one embodiment：The graphite powder is the mixing of one or both of crystalline graphite powder, expanded graphite powder.Graphite
The purity of powder is higher, and obtained graphite olefinic impurity is fewer, such as high purity graphite powder effect is preferable.
In one embodiment：The intercalator is solid-solid inorganic salt, preferably one in ammonium hydrogen carbonate solid, ammonium carbonate solid
Kind or two kinds of mixing, ammonium hydrogen carbonate, ammonium carbonate are completely decomposed into ammonia and carbon dioxide by heat energy, do not have solid residue,
Also it can guarantee that and produce enough gas flows and impulsive force；But the species of intercalator is not limited thereto, can be heated complete decomposition
Other solid inorganic salts and SOLID ORGANIC salt for gas etc. can also use as intercalator.
In one embodiment：The equipment that the ball milling uses is stirring ball mill or planetary ball mill.
In one embodiment：The material of the ball grinder is polytetrafluoroethylene (PTFE), stainless steel or ceramics.
In one embodiment：The material of the mill ball is zirconia ball, ceramics, steel ball, glass or agate ball, and mill ball exists
It can not be got off during ball milling by mill, and material is different, density is different, and impulsive force also can be different, corresponding obtained graphite powder
Particle diameter differs, and produces different edge defect, mixing intercalation effect is also different, with the ball milling effect of zirconia ball and agate ball
Preferably.
In one embodiment：The sealing reactor is the stainless steel water thermal response of the polytetrafluoroethyllining lining of high temperature high voltage resistant
Kettle.
Compared with background technology, it has the following advantages that the technical program：
1. the quick method for preparing high-quality graphene of the present invention pertains only to making for graphite powder and two kinds of materials of intercalator
With using graphite powder as presoma, and whole preparation process is carried out all in solid phase, avoids a series of making for chemical reagent
With green pollution-free.
2. the present invention is filled using the intercalator of the heated complete polarity gas molecule of decomposition and inversion of meeting using heated sealed
Processing is put, effectively using polar gas molecular action caused by its decomposition, promotes effective intercalation, gas molecule breaks through graphite layers
Van der Waals force, then graphite is efficiently peeled off by microwave radiation technology and becomes uniform graphene film, whole preparation process is not related to oxygen
Change reduction reaction, it is easy to operate, rapidly and efficiently；Obtained graphene-structured is complete, defect is less, and oxygen content is low, high-yield high-quality.
3. the present invention prepares graphene process and carried out in solid phase, without using chemical reagent, it also avoid filtering, wash
The operation such as wash, disperse, can effectively avoid the generation of graphene secondary agglomeration, the graphene sheet layer effect prepared is good, defect
It is few.
4. instrument and equipment involved in the present invention is simply common, there is the advantages of cost is low, easy to spread, be particularly suitable for use in
Large-scale industrial production.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM figures) for the graphene sample that experimental example 1 of the present invention is prepared.
Fig. 2 is the transmission electron microscope picture (TEM figures) for the graphene sample that experimental example 1 of the present invention is prepared.
Fig. 3 is the XPS test result schematic diagrames for the graphene sample that the embodiment of the present invention 1 is prepared.
Fig. 4 is that the raw material that the embodiment of the present invention 3 uses is 8000 mesh crystalline graphite powders and the graphene being finally prepared
The Raman spectrum comparison diagram of sample.
Fig. 5 is that the raw material that the embodiment of the present invention 3 uses is 8000 mesh crystalline graphite powders (a), (b) and is finally prepared
ESEM (SEM) figure of graphene sample (c), (d).
Fig. 6 is that the TEM for the graphene that the embodiment of the present invention 3 is prepared schemes (a) and HRTEM schemes (b).
Embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1
1) using the crystalline graphite powder of 80 mesh as raw material, using ammonium hydrogen carbonate solid as intercalator, according to graphite powder and intercalation
The mass ratio of agent is 1:4 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into stainless steel jar mill, according to ratio of grinding media to material 6~20:1 adds
400g zirconium dioxide mill balls not of uniform size, and 1/3~2/3 that total charge is ball milling tank volume is controlled, in ball mill
In with 90r/min rotating speed stirring ball-milling 1h, obtain uniform black solid mixture；
3) stainless steel water that the black solid mixture obtained in step 2) is placed in polytetrafluoroethyllining lining heats seal instead
Answer in kettle, 2h is heated in the vacuum drying oven that temperature is 60 DEG C, take out, after being cooled to room temperature, transfer in ceramic crucible, put
Enter micro-wave oven, 5min is heated with middle high fiery (power about 800~1200W) microwave, that is, obtains the graphene of solid.
ESEM (SEM) figure of graphene obtained by the present embodiment and with transmission electron microscope (TEM) figure respectively such as Fig. 1, Fig. 2
It is shown, it can substantially observe gained graphene sample in uniformly large stretch of lamellar structure from figure.
Graphene XPS test results schematic diagram obtained by the present embodiment as shown in figure 3, its oxygen content few (being less than 5%) i.e.
Oxygen-containing functional group is far less than graphene prepared by general conventional oxidation reducing process.
Embodiment 2
1) using the crystalline graphite powder of 80 mesh as raw material, using ammonium hydrogen carbonate solid as intercalator, according to graphite powder and intercalation
The mass ratio of agent is 1:20 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into stainless steel jar mill, according to ratio of grinding media to material 6~20:1 adds
400g zirconium dioxide mill balls not of uniform size, and 1/3~2/3 that total charge is ball milling tank volume is controlled, in ball mill
In with 100r/min rotating speed stirring ball-milling 1h, obtain uniform black solid mixture；
3) stainless steel water that the black solid mixture obtained in step 2) is placed in polytetrafluoroethyllining lining heats seal instead
Answer in kettle, 2h is heated in the vacuum drying oven that temperature is 80 DEG C, take out, after being cooled to room temperature, transfer in ceramic crucible, put
Enter micro-wave oven, 3min is heated with middle high fiery (power about 800~1200W) microwave, that is, obtains the graphene of solid.
Embodiment 3
1) using the crystalline graphite powder of 8000 mesh as raw material, using ammonium hydrogen carbonate solid as intercalator, according to graphite powder with inserting
The mass ratio of layer agent is 1:20 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into stainless steel jar mill, according to ratio of grinding media to material 6~20:1 adds
400g zirconium dioxide mill balls not of uniform size, and 1/3~2/3 that total charge is ball milling tank volume is controlled, in ball mill
In with 90r/min rotating speed stirring ball-milling 1h, obtain uniform black solid mixture；
3) stainless steel water that the black solid mixture obtained in step 2) is placed in polytetrafluoroethyllining lining heats seal instead
Answer in kettle, 2h is heated in the vacuum drying oven that temperature is 70 DEG C, take out, after being cooled to room temperature, transfer in ceramic crucible, put
Enter micro-wave oven, 5min is heated with middle high fiery (power about 800~1200W) microwave, that is, obtains the graphene of solid.
Graphene and the Raman comparison diagram of raw graphite powder contrast obtained by the present embodiment, ESEM (SEM) figure difference
Such as Fig. 4, shown in Fig. 5.See from Raman comparison diagram, the I of sample before and after microwaveD/IGIntensity than not obvious difference, its
The defects of causing is little, but 2D peaks are but offset there occurs obvious, by the 2917cm of raw material-1It is offset to 2882cm-1, illustrate this
Case, which is successfully peeled off, obtains few layer of graphene.Simultaneously from Fig. 4 ESEM comparison diagram, can visually see graphite powder
It has been efficiently peeled off into flake structure, and lamella effect keeps good.In addition, the graphene sample that the present embodiment obtains
TEM is schemed with HRTEM (high resolution TEM) figures as shown in fig. 6, can further will become apparent from graphene sample sheet and lack
Rotating fields.
Embodiment 4
1) using the crystalline graphite powder of 8000 mesh as raw material, using ammonium hydrogen carbonate solid as intercalator, according to graphite powder with inserting
The mass ratio of layer agent is 1:10 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into stainless steel jar mill, according to ratio of grinding media to material 6~20:1 adds
400g zirconium dioxide mill balls not of uniform size, and 1/3~2/3 that total charge is ball milling tank volume is controlled, in ball mill
In with 90r/min rotating speed stirring ball-milling 2h, obtain uniform black solid mixture；
3) stainless steel water that the black solid mixture obtained in step 2) is placed in polytetrafluoroethyllining lining heats seal instead
Answer in kettle, 2h is heated in the vacuum drying oven that temperature is 70 DEG C, take out, after being cooled to room temperature, transfer in ceramic crucible, put
Enter micro-wave oven, 3min is heated with middle high fiery (power about 800~1200W) microwave, that is, obtains the graphene of solid.
Embodiment 5
1) using expanded graphite powder as raw material, using ammonium hydrogen carbonate solid as intercalator, according to the matter of graphite powder and intercalator
Amount is than being 1:20 ratio, it is standby after graphite powder and intercalator premixing uniformly；
2) mixture after being pre-mixed in step 1) is put into stainless steel jar mill, according to ratio of grinding media to material 6~20:1 adds
400g zirconium dioxide mill balls not of uniform size, and 1/3~2/3 that total charge is ball milling tank volume is controlled, in ball mill
In with 90r/min rotating speed stirring ball-milling 2h, obtain uniform black solid mixture；
3) stainless steel water that the black solid mixture obtained in step 2) is placed in polytetrafluoroethyllining lining heats seal instead
Answer in kettle, 2h is heated in the vacuum drying oven that temperature is 70 DEG C, take out, after being cooled to room temperature, transfer in ceramic crucible, put
Enter micro-wave oven, 3min is heated with middle high fiery (power about 800~1200W) microwave, that is, obtains the graphene of solid.
It is described above, only present pre-ferred embodiments, therefore the scope that the present invention is implemented can not be limited according to this, i.e., according to
The equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still it belong in the range of the present invention covers.
Claims (6)
- A kind of 1. quick method for preparing high-quality graphene, it is characterised in that：It is not related to redox reaction, including：1) using graphite powder as raw material, the mass ratio according to solid-state intercalator of the graphite powder with that can resolve into gas completely after being heated is 1:1~1:40 ratio, it is standby after graphite powder and intercalator premixing uniformly；The intercalator is ammonium hydrogen carbonate solid, carbon The mixing of one or both of sour ammonium solid；2) mixture after being pre-mixed in step 1) is put into ball grinder, according to ratio of grinding media to material 6~20:1 addition is not of uniform size Mill ball, and 1/3~2/3 that total charge is ball milling tank volume is controlled, with 80~120r/min rotating speed stirring ball-milling 0.25~2h, graphite powder is produced in edge defect and intercalator insertion graphite powder by ball milling and realize intercalation, obtain intercalator Physics intercalated graphite mixture, in uniform black solid mixture；3) the black solid mixture obtained in step 2) is first placed in sealing reactor, in the vacuum that temperature is 40~90 DEG C 20min~6h is heated in baking oven and promotes intercalation；Take out, after being cooled to room temperature, transfer in microwave equipment with 100~1200W Power microwave heat 0.05~10min, obtain solid graphite alkene.
- 2. according to the method for claim 1, it is characterised in that：The graphite powder is in crystalline graphite powder, expanded graphite powder One or two kinds of mixing.
- 3. the quick method for preparing high-quality graphene according to claim 1, it is characterised in that：The material of the mill ball Matter is zirconia ball, ceramics, steel ball, glass or agate ball.
- 4. the quick method for preparing high-quality graphene according to claim 1, it is characterised in that：What the ball milling used Equipment is stirring ball mill or planetary ball mill.
- 5. the quick method for preparing high-quality graphene according to claim 1, it is characterised in that：The material of the ball grinder Matter is polytetrafluoroethylene (PTFE), stainless steel or ceramics.
- 6. the quick method for preparing high-quality graphene according to claim 1, it is characterised in that：The sealing reactor For the stainless steel hydrothermal reaction kettle of the polytetrafluoroethyllining lining of high temperature high voltage resistant.
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