CN105800603A - Method for quickly preparing high-quality graphene - Google Patents
Method for quickly preparing high-quality graphene Download PDFInfo
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- 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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- 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 method for quickly preparing high-quality graphene. Graphite powder and solid intercalator which can be fully decomposed into gas after being heated are mixed, ball-milled and properly heated to realize intercalation, then 100 to 1200W microwave radiation treatment is performed for 0.05 to 10min, the intercalator is fully decomposed into gas at a high temperature, and gas molecules seep into graphite sheets and overcome Van der Waals force between the graphite sheets to enable graphite to be effectively stripped. The method for quickly preparing high-quality graphene has the advantages of simple preparation process, low manufacturing cost, convenience in process operation, quickness and high efficiency, environment friendliness, high product quality, easiness in large-scale use and the like.
Description
Technical field
The invention belongs to field of inorganic materials, be specifically related to a kind of method quickly preparing high-quality graphene.
Background technology
Since professor Geim from Univ Manchester UK in 2004 etc. adopt adhesive tape stripping method to separate Graphene first from graphite, Graphene is with the structure of its uniqueness, character and potential application, increasingly cause the extensive concern of research worker, and have become as the focus of the various fields researchs such as material, chemistry, physics.In recent years, scientific research personnel develops numerous method preparing Graphene, wherein mainly includes mechanical stripping method, chemical vapour deposition (CVD) (CVD), epitaxial growth and oxidation-reduction method etc..Its controllability of mechanical stripping method is poor, and the Graphene prepared is smaller and there is very big uncertainty, and efficiency is low simultaneously, is not suitable for large-scale production.In order to overcome this shortcoming, can successfully preparing large-area graphene film by CVD, but CVD treatment conditions are harsh, operating process is more complicated, and energy expenditure is big and is not suitable for large-scale production.On the other hand, uniform graphene platelet can be prepared in large area by epitaxial growth method, but the major defect cost of this method is high, and need to carry out in high temperature.The most common method that oxidation-reduction method is prepared as Graphene, it is also considered as the most promising method for commercial production Graphene.But, this method still has a lot of problems on expanding production, as reduced control, purifying products and environmental pollution etc..
Therefore, how low cost, quickly preparing high-quality Graphene is still a study hotspot and a difficult problem expeditiously.In order to develop a kind of fast preparation method to realize the extensive preparation of Graphene, researcheres are by constantly experimental exploring, finding can the warm-up movement of the oxy radical such as hydroxyl (-OH), carboxyl (-COOH) on induced oxidation graphite by microwave radiation, these oxygen-containing functional groups are made to decompose, decompose and produce substantial amounts of micro-molecular gas, it is thus possible to overcome the Van der Waals force of oxidized graphite flake interlayer, it is achieved the quick stripping of oxidized graphite flake layer, it is thus achieved that Graphene.Chen etc. report the graphene oxide in the mixed solution utilizing microwave radiation to will be dispersed in DMF and water to carry out Rapid Thermal reduction and obtains the Graphene (Carbon, 2010,48 (4): 1146-1152) of reduction.
The heating advantage being rapidly heated owing to microwave radiation is all even, it has been proposed as efficient heating means for quickly preparing Graphene, and prepared by the stripping being effectively realized Graphene under some adjuvant effects.Janowska etc. report and are dispersed in ammonia spirit using expanded graphite after supersound process a period of time as presoma, again it is carried out microwave heating and synthesize the graphene film (NanoResearch of large stretch of few layer, 2010,3 (2): 126-137).CN201310036671 discloses a kind of method that in air atmosphere, rapid thermal treatment prepares Graphene, and the method adopts graphene oxide as presoma, after mixing with nitrogen-containing compound, is prepared the graphene powder of N doping by microwave rapid thermal treatment.Ye etc. utilize graphite oxide (GO) and ammonium hydrogen carbonate prepared by Hummers method as presoma, and when Microwave-assisted firing, Graphene (Carbon, 2012,50 (6): 2134-2140) is prepared in fast restore and stripping.The at present research of these Microwave-assisted Reductions is concentrated mainly on the graphite oxide or graphene oxide that use pretreatment and synthesizes as presoma or by liquid chromatography ultrasound.In these preprocessing process, the time is longer; inevitably relate to simultaneously a series of chemical reagent use; it is unfavorable for environmental conservation; and the Graphene defect produced is relatively more; its intrinsic property receives certain destruction; therefore for widening the effect of Graphene application, the quick preparation of intrinsic Graphene need to be realized further by non-oxidation or weak oxide, to meet industrialization production requirements.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art part, provide a kind of method quickly preparing high-quality graphene, it is not related to oxidoreduction path, environmental protection, with low cost, simple to operate, rapidly and efficiently, the graphene-structured obtained is complete, defect is less, oxygen content is low, is suitable for large-scale promotion.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of method quickly preparing high-quality graphene, including:
1) with graphite powder for raw material, according to graphite powder be heated after can resolve into the ratio that mass ratio is 1:1～1:40 of solid-state intercalator of gas completely, by after graphite powder and intercalator premixing uniformly, standby；
2) by step 1) in mixture after premixing put in ball grinder, mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and the cumulative volume controlling total charge and mixture and mill ball be ball grinder volume 1/3～2/3, rotating speed stirring ball-milling 0.25～2h with 80～120r/min, graphite powder is made to produce edge defect by ball milling, it is easy to intercalator and embeds in graphite powder, the two is made to realize mixing intercalation, obtain intercalator physics intercalated graphite mixture, in uniform black solid mixture；Using mill ball not of uniform size, different size cooperates, it is possible to ball milling obtains the graphite powder that particle diameter differs, so that graphite powder produces the edge defect differed, thus promoting that intercalator embeds in graphite powder to realize mixing better intercalation；Namely commercially available mill ball has combination not of uniform size；
3) by step 2) in the black solid mixture that obtains be placed in microwave equipment and heat 0.05～10min with the power microwave of 100～1200W, obtain solid graphite alkene.
Preferably, described step 3) in, by step 2) in the black solid mixture that obtains first be placed in sealed reactor, the vacuum drying oven that temperature is 40～90 DEG C heats 20min～6h, take out, after being cooled to room temperature, transfer in microwave equipment and heat 0.05～10min with the power microwave of 100～1200W, solid graphite alkene can be obtained when not producing redox reaction.
First heating under the lower temperature of 40～90 DEG C, temperature is height not very, and intercalator will not decompose in a large number under this temperature conditions, also would not produce enough gas, it is possible to prevent graphite from peeling off；Meanwhile, certain temperature can promote molecular motion, promotes graphite powder to realize effectively mixing intercalation with intercalator further, obtains high-quality intercalator physics intercalated graphite mixture；In sealed reactor, heating is prevented from a small amount of intercalator resolving into gas and loses because of gaseous volatilization, these decomposed intercalators can recover again the solid state before decomposing after cooling, thus ensureing the amount of intercalator and the peeling effect of follow-up microwave treatment.
After above-mentioned heating steps promotes intercalation, coordinate microwave heating again, microwave heating has homogeneous temperature relative to traditional heating, the effect that temperature rising is fast, the hot environment quickly produced can make intercalator thoroughly decompose completely rapidly and produce a large amount of gases, add the microwave expansion to graphite, make intercalator decompose a large amount of gas molecules obtained at short notice can rapidly permeate in graphite flake layer, and the Height Impact power that gas produces in a large number can overcome rapidly the Van der Waals force between graphite flake layer, thus realizing the quick of graphite, completely strip, obtain in uniform large stretch of flake structure, and lamella effect keeps good structural integrity, defect is less, hypoxic high-quality graphene.
The power of described microwave is 100～1200W, and correspondingly, microwave heating time is 0.05～10min；Power is more high, and heating rate is fast, and heat time heating time shortens accordingly, and intercalator can decompose a large amount of gases of generation at short notice completely, and the impulsive force of generation is big, peeling effect and in hgher efficiency；Power is more low, and heat time heating time extends accordingly.The microwave equipment adopted is such as microwave oven；The power of microwave oven is referred to microwave oven description and converts.
In one embodiment: described graphite powder is one or both the mixing in crystalline graphite powder, expanded graphite powder.The purity of graphite powder is more high, and the Graphene impurity obtained is more few, for instance high purity graphite powder effect is better.
In one embodiment: described intercalator is solid-solid inorganic salt, it is preferably one or both the mixing in ammonium hydrogen carbonate solid, ammonium carbonate solid, ammonium hydrogen carbonate, ammonium carbonate are completely decomposed into ammonia and carbon dioxide by heat energy, do not have solid residue, can guarantee that the enough gas flows of generation and impulsive force yet；But the kind of intercalator is not limited thereto, it is possible to be heated other solid inorganic salts being completely decomposed into gas and SOLID ORGANIC salt etc. also can use as intercalator.
In one embodiment: the equipment that described ball milling adopts is stirring ball mill or planetary ball mill.
In one embodiment: the material of described ball grinder is politef, rustless steel or pottery.
In one embodiment: the material of described mill ball is zirconia ball, pottery, steel ball, glass or agate ball, mill ball can not be ground in the process of ball milling, and material is different, density is different, impulsive force also can be different, and the graphite powder particle diameter that correspondence obtains 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: described sealed reactor is the teflon-lined rustless steel hydrothermal reaction kettle of high temperature high voltage resistant.
The technical program is compared with background technology, and it has the advantage that
1. the method quickly preparing high-quality graphene of the present invention pertains only to graphite powder and the use of two kinds of materials of intercalator, using graphite powder as presoma, and whole preparation process all carries out in solid phase, it is to avoid the use of a series of chemical reagent, environmental protection is pollution-free.
2. the present invention adopts the intercalator of the meeting polarity gas molecule of complete decomposition and inversion that is heated, and adopt heated sealed device to process, it is effectively utilized to decompose the polar gas molecular action produced, promote effective intercalation, gas molecule breaks through graphite layers Van der Waals force, is efficiently peeled off by graphite again through microwave-assisted and becomes uniform graphene film, and whole preparation process is not related to redox reaction, easy to operate, rapidly and efficiently；The graphene-structured obtained is complete, defect is less, and oxygen content is low, high-yield high-quality.
3. the present invention prepares Graphene process and carries out in solid phase, it is not necessary to use chemical reagent, it also avoid the operations such as sucking filtration, washing, dispersion, it is possible to being prevented effectively from the generation of Graphene secondary agglomeration, the graphene sheet layer prepared is effective, and defect is few.
4. instrument and equipment involved in the present invention is simply common, has the advantage that cost is low, easy to spread, is particularly suited for large-scale commercial production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM figure) of the Graphene sample that experimental example 1 of the present invention prepares.
Fig. 2 is the transmission electron microscope picture (TEM figure) of the Graphene sample that experimental example 1 of the present invention prepares.
Fig. 3 is the XPS test result schematic diagram of the Graphene sample that the embodiment of the present invention 1 prepares.
Fig. 4 is the raw material i.e. 8000 order crystalline graphite powders that the embodiment of the present invention 3 adopts and the Raman spectrum comparison diagram of Graphene sample finally prepared.
Fig. 5 is scanning electron microscope (SEM) figure of raw material i.e. 8000 orders crystalline graphite powder (a), (b) and Graphene sample (c) finally prepared, (d) that the embodiment of the present invention 3 adopts.
Fig. 6 is TEM figure (a) and HRTEM figure (b) of the Graphene that the embodiment of the present invention 3 prepares.
Detailed description of the invention
Illustrate present disclosure by the examples below:
Embodiment 1
1) with the crystalline graphite powder of 80 orders for raw material, using ammonium hydrogen carbonate solid as intercalator, according to the ratio that mass ratio is 1:4 of graphite powder Yu intercalator, after uniform to graphite powder and intercalator premixing, standby；
2) by step 1) in mixture after premixing put in stainless steel jar mill, 400g zirconium dioxide mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, with the rotating speed stirring ball-milling 1h of 90r/min in ball mill, obtain uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in teflon-lined stainless steel water heat seal reactor, the vacuum drying oven that temperature is 60 DEG C heats 2h, take out, after being cooled to room temperature, transfer in ceramic crucible, put into microwave oven, with middle high fire (power is 800～1200W about) microwave heating 5min, namely obtain the Graphene of solid.
Scanning electron microscope (SEM) figure of the Graphene of the present embodiment gained and and transmission electron microscope (TEM) figure respectively as shown in Fig. 1, Fig. 2, can substantially observe the gained Graphene sample lamellar structure in uniformly sheet from figure.
The Graphene XPS test result schematic diagram of the present embodiment gained is as it is shown on figure 3, the Graphene prepared far less than general conventional oxidation reducing process of its oxygen content few (lower than 5%) i.e. oxygen-containing functional group.
Embodiment 2
1) with the crystalline graphite powder of 80 orders for raw material, using ammonium hydrogen carbonate solid as intercalator, according to the ratio that mass ratio is 1:20 of graphite powder Yu intercalator, after uniform to graphite powder and intercalator premixing, standby；
2) by step 1) in mixture after premixing put in stainless steel jar mill, 400g zirconium dioxide mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, with the rotating speed stirring ball-milling 1h of 100r/min in ball mill, obtain uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in teflon-lined stainless steel water heat seal reactor, the vacuum drying oven that temperature is 80 DEG C heats 2h, take out, after being cooled to room temperature, transfer in ceramic crucible, put into microwave oven, with middle high fire (power is 800～1200W about) microwave heating 3min, namely obtain the Graphene of solid.
Embodiment 3
1) with the crystalline graphite powder of 8000 orders for raw material, using ammonium hydrogen carbonate solid as intercalator, according to the ratio that mass ratio is 1:20 of graphite powder Yu intercalator, after uniform to graphite powder and intercalator premixing, standby；
2) by step 1) in mixture after premixing put in stainless steel jar mill, 400g zirconium dioxide mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, with the rotating speed stirring ball-milling 1h of 90r/min in ball mill, obtain uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in teflon-lined stainless steel water heat seal reactor, the vacuum drying oven that temperature is 70 DEG C heats 2h, take out, after being cooled to room temperature, transfer in ceramic crucible, put into microwave oven, with middle high fire (power is 800～1200W about) microwave heating 5min, namely obtain the Graphene of solid.
The Raman comparison diagram that the Graphene of the present embodiment gained contrasts with raw graphite powder, scanning electron microscope (SEM) figure is respectively as shown in Fig. 4, Fig. 5.See from Raman comparison diagram, the I of sample before and after microwaveD/IGStrength ratio is significantly difference not, and its defect caused is little, but 2D peak but there occurs obvious skew, by the 2917cm of raw material-1It is offset to 2882cm-1, illustrate that present case successfully peels off the Graphene obtaining few layer.Simultaneously from the scanning electron microscope comparison diagram of Fig. 4, it is possible to find out that graphite powder has been efficiently peeled off into flake structure intuitively, and lamella effect keeps good.It addition, TEM figure and HRTEM (high resolution TEM) figure of the Graphene sample that obtains of the present embodiment is as shown in Figure 6, Graphene sample sheet and few Rotating fields can be will become apparent from further.
Embodiment 4
1) with the crystalline graphite powder of 8000 orders for raw material, using ammonium hydrogen carbonate solid as intercalator, according to the ratio that mass ratio is 1:10 of graphite powder Yu intercalator, after uniform to graphite powder and intercalator premixing, standby；
2) by step 1) in mixture after premixing put in stainless steel jar mill, 400g zirconium dioxide mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, with the rotating speed stirring ball-milling 2h of 90r/min in ball mill, obtain uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in teflon-lined stainless steel water heat seal reactor, the vacuum drying oven that temperature is 70 DEG C heats 2h, take out, after being cooled to room temperature, transfer in ceramic crucible, put into microwave oven, with middle high fire (power is 800～1200W about) microwave heating 3min, namely obtain the Graphene of solid.
Embodiment 5
1) with expanded graphite powder for raw material, using ammonium hydrogen carbonate solid as intercalator, according to the ratio that mass ratio is 1:20 of graphite powder Yu intercalator, after uniform to graphite powder and intercalator premixing, standby；
2) by step 1) in mixture after premixing put in stainless steel jar mill, 400g zirconium dioxide mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, with the rotating speed stirring ball-milling 2h of 90r/min in ball mill, obtain uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in teflon-lined stainless steel water heat seal reactor, the vacuum drying oven that temperature is 70 DEG C heats 2h, take out, after being cooled to room temperature, transfer in ceramic crucible, put into microwave oven, with middle high fire (power is 800～1200W about) microwave heating 3min, namely obtain the Graphene of solid.
The above, be only present pre-ferred embodiments, therefore can not limit scope of the invention process according to this, and the equivalence namely made according to the scope of the claims of the present invention and description changes and modifies, and all should still belong in the scope that the present invention contains.
Claims (9)
1. the method quickly preparing high-quality graphene, it is characterised in that: it is not related to redox reaction, including:
1) with graphite powder for raw material, according to graphite powder be heated after can resolve into the ratio that mass ratio is 1:1～1:40 of solid-state intercalator of gas completely, by after graphite powder and intercalator premixing uniformly, standby；
2) by step 1) in mixture after premixing put in ball grinder, mill ball not of uniform size is added according to ratio of grinding media to material 6～20:1, and control total charge be ball grinder volume 1/3～2/3, rotating speed stirring ball-milling 0.25～2h with 80～120r/min, make graphite powder produce edge defect by ball milling and intercalator embeds in graphite powder and realizes intercalation, obtain intercalator physics intercalated graphite mixture, in uniform black solid mixture；
3) by step 2) in the black solid mixture that obtains be placed in microwave equipment and heat 0.05～10min with the power microwave of 100～1200W, obtain solid graphite alkene.
2. method according to claim 1, it is characterised in that: described step 3) in, by step 2) in the black solid mixture that obtains first be placed in sealed reactor, the vacuum drying oven that temperature is 40～90 DEG C heats 20min～6h and promotes intercalation；Take out, after being cooled to room temperature, transfer in microwave equipment and heat 0.05～10min with the power microwave of 100～1200W, obtain solid graphite alkene.
3. method according to claim 1 and 2, it is characterised in that: described graphite powder is one or both the mixing in crystalline graphite powder, expanded graphite powder.
4. method according to claim 1 and 2, it is characterised in that: described intercalator is solid-solid inorganic salt.
5. method according to claim 4, it is characterised in that: described intercalator is one or both the mixing in ammonium hydrogen carbonate solid, ammonium carbonate solid.
6. the method quickly preparing high-quality graphene according to claim 1, it is characterised in that: the material of described mill ball is zirconia ball, pottery, steel ball, glass or agate ball.
7. the method quickly preparing high-quality graphene according to claim 1, it is characterised in that: the equipment that described ball milling adopts is stirring ball mill or planetary ball mill.
8. the method quickly preparing high-quality graphene according to claim 1, it is characterised in that: the material of described ball grinder is politef, rustless steel or pottery.
9. the method quickly preparing high-quality graphene according to claim 2, it is characterised in that: described sealed reactor is the teflon-lined rustless steel hydrothermal reaction kettle of high temperature high voltage resistant.
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